Organic electroluminescent materials and devices

Abstract

The invention relates to organic electroluminescent materials and devices. The present invention provides an organic electroluminescent device (OLED) comprising an anode; a cathode; and an emission region including a first emission layer disposed between the anode and the cathode. The OLED further comprises a microcavity structure, the first emission layer comprising a first emitter which is a phosphorescent emitter or a fluorescent emitter; when a voltage is applied on the OLED, the first emission layer emits first light-emitting radiation; the first emission layer has a photoluminescence spectrum having a peak emission wavelength [lambda] max, a first area T and a second area M; the OLED has the brightness of l0 under normal incidence and has the brightness of l60 under the condition that an angle of 60 degrees is formed between the OLED and the normal incidence; and one of the following conditions is true: (1) the first emitter is a phosphorescent emitter with an M / T ratio > = 0.38 and 160 / 10 > = 15%; or (2) the first emitter is a fluorescent emitter with an M / T ratio > = 0.42 and 160 / 10 > = 25%.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application No. 63 / 591,653, filed on October 19, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to novel device architectures and OLED devices having those novel architectures and their uses. Background Art

[0004] Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many materials used to manufacture the devices are relatively inexpensive, so organic optoelectronic devices have the potential to have cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) can make them more suitable for specific applications, such as manufacturing on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

[0005] OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly attractive technology for use in applications such as flat panel displays, lighting, and backlighting.

[0006] One application of phosphorescent emitting molecules is full-color displays. Industry standards for such displays require pixels that are suitable for emitting specific colors (called "saturated" colors). Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, an absorption filter is used to filter the emission from a white backlight to produce red, green, and blue emissions. The same technology can also be used for OLEDs. White OLEDs can be single-emission layer (EML) devices or stacked structures. Color can be measured using CIE coordinates well known in the art. Summary of the invention

[0007] In one aspect, an organic electroluminescent device (OLED) is provided, comprising an anode; a cathode; and an emission region, the emission region comprising a first emission layer disposed between the anode and the cathode. The OLED further comprises a microcavity structure, and:

[0008] The first emitting layer comprises a first emitter selected from the group consisting of: a phosphorescent emitter and a fluorescent emitter;

[0009] When a voltage is applied to the OLED, the first emitting layer emits a first luminescent radiation at room temperature;

[0010] The first emission layer has a photoluminescence spectrum having a peak emission wavelength λ max , a first area T and a second area M;

[0011] where T is the total integrated area of ​​the photoluminescence spectrum, and M is in λ max -15nm and λ max The integrated area of ​​the photoluminescence spectrum between +15 nm;

[0012] The OLED has a brightness of l0 at normal incidence and a brightness of l at 60 degrees from normal incidence. 60 ;and

[0013] One of the following conditions is true:

[0014] (1) The first emitter is a phosphorescent emitter, wherein M / T ≥ 0.38 and l 60 / l0≥15%;

[0015] (2) The first emitter is a fluorescent emitter, wherein M / T ≥ 0.42 and l 60 / l0≥25%. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 An organic light emitting device is shown.

[0017] Figure 2 An inverted organic light-emitting device without a separate electron transport layer is demonstrated.

[0018] Figure 3 Shown are plots of modeled P-polarized photoluminescence versus angle for emitters with different vertical dipole ratio (VDR) values. DETAILED DESCRIPTION

[0019] A. Terminology

[0020] Unless otherwise specified, the following terms used herein are defined as follows:

[0021] As used herein, "top" means farthest from the substrate, while "bottom" means closest to the substrate. Where a first layer is described as being "disposed "above" a second layer, the first layer is disposed farther from the substrate. Unless it is specified that the first layer is "in contact with" the second layer, there may be other layers between the first and second layers. For example, a cathode may be described as being "disposed "above" an anode even though various organic layers are present between the cathode and the anode.

[0022] As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and / or deposited from a liquid medium in the form of a solution or suspension.

[0023] As used herein, and as will be generally understood by one skilled in the art, a first "Highest Occupied Molecular Orbital" (HOMO) or "Lowest Unoccupied Molecular Orbital" (LUMO) energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since the ionization potential (IP) is measured as a negative energy relative to the vacuum energy level, a higher HOMO energy level corresponds to an IP with a smaller absolute value (a less negative IP). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value (a less negative EA). On a conventional energy level diagram with the vacuum energy level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A "higher" HOMO or LUMO energy level appears closer to the top of this diagram than a "lower" HOMO or LUMO energy level.

[0024] As used herein, and as one skilled in the art would generally understand, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Because work functions are typically measured as negative numbers relative to the vacuum level, this means that a "higher" work function is more negative. On a conventional energy level diagram with the vacuum level at the top, a "higher" work function is illustrated as being farther away from the vacuum level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows different rules than work functions.

[0025] The terms "halo," "halogen," and "halo" are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

[0026] The term "acyl" refers to a substituted carbonyl (-C(O)-R s ).

[0027] The term "ester" refers to a substituted oxycarbonyl (-OC(O)-R s OR-C(O)-OR s ) group.

[0028] The term "ether" refers to -OR s Group.

[0029] The terms "thio" or "thioether" are used interchangeably and refer to -SR s Group.

[0030] The term "selenoalkyl" refers to -SeR s Group.

[0031] The term "sulfinyl" refers to -S(O)-R s Group.

[0032] The term "sulfonyl" refers to -SO2-R s Group.

[0033] The term "phosphino" refers to a group containing at least one phosphorus atom, which is used to bond to the relevant molecule, common examples such as but not limited to -P(R s )2 group or -PO(R s )2 group, wherein each R s Can be the same or different.

[0034] The term "silyl group" refers to a group containing at least one silicon atom, which is used to bond to the relevant molecule, common examples such as but not limited to -Si(R s )3 groups, wherein each R s Can be the same or different.

[0035] The term "germanyl" refers to a group containing at least one germanium atom, which is used to bond to the relevant molecule, common examples such as but not limited to -Ge(R s )3 groups, wherein each R s Can be the same or different.

[0036] The term "boryl" refers to a group containing at least one boron atom that is used to bond to the relevant molecule, common examples of which are, but not limited to, -B(R s )2 group or its Lewis adduct -B(R s )3 groups, wherein R s Can be the same or different.

[0037] In each of the above, R s It can be hydrogen or a common substituent as defined in the present application. s is selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. More preferably, R s Selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0038] The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing one to fifteen carbon atoms, preferably one to nine carbon atoms, and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. In addition, the alkyl group may be further substituted.

[0039] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 3 to 12 ring carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. In addition, the cycloalkyl group may be further substituted.

[0040] The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge and Se, preferably O, S or N. In addition, the heteroalkyl or heterocycloalkyl group may be optionally substituted.

[0041] The term "alkenyl" refers to and includes straight and branched alkenyls. Alkenyls are essentially alkyls that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyls are essentially cycloalkyls that include at least one carbon-carbon double bond in the cycloalkyl ring. As used herein, the term "heteroalkenyl" refers to an alkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si, Ge and Se, preferably O, S or N. Preferred alkenyls, cycloalkenyls or heteroalkenyls are those containing two to fifteen carbon atoms. In addition, alkenyls, cycloalkenyls or heteroalkenyls may be further substituted.

[0042] The term "alkynyl" refers to and includes straight and branched chain alkynyl groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are alkynyl groups containing two to fifteen carbon atoms. In addition, alkynyl groups may be further substituted.

[0043] The terms "aralkyl" or "arylalkyl" are used interchangeably and refer to an alkyl group substituted with an aryl group. Additionally, the aralkyl group may be further substituted.

[0044] The term "heterocyclic group" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge and Se, preferably O, S, N or B. Aromatic heterocyclic groups can be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 10 ring atoms, preferably heterocyclic groups containing 3 to 7 ring atoms, including at least one heteroatom, and including cyclic amines, such as morpholinyl, piperidinyl, pyrrolidinyl, etc., and cyclic ethers / thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, etc. In addition, the heterocyclic group can be further substituted.

[0045] The term "aryl" refers to and includes monocyclic and polycyclic aromatic hydrocarbon groups. Polycyclic rings may have two or more rings in which two carbons are common to two adjacent rings (the rings are "fused"). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene and naphthalene. In addition, the aryl group may be further substituted or fused, such as but not limited to fluorene.

[0046] The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to, O, S, Se, N, P, B, Si, Ge, and Se. In many cases, O, S, N, or B are preferred heteroatoms. Monocyclic heteroaromatic systems are preferably monocyclic rings with 5 or 6 ring atoms, and the rings may have one to six heteroatoms. Heteropolycyclic ring systems may have two or more aromatic rings in which two atoms are common to two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl. Heteropolycyclic aromatic ring systems may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryls are heteroaryls containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridyl indole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazole In some embodiments, the heteroaryl group may be substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof. In some embodiments, the heteroaryl group may be substituted with 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine and aza analogs thereof.

[0047] Among the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine and benzimidazole and their respective corresponding aza analogs are of particular interest.

[0048] In many cases, the universal substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0049] In some cases, preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

[0050] In some cases, more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silanyl, aryl, heteroaryl, nitrile, thio, and combinations thereof.

[0051] In some cases, more preferred universal substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silane, aryl, heteroaryl, nitrile, and combinations thereof.

[0052] In other cases, the most preferred universal substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

[0053] The terms "substituted" and "substituted" refer to the bonding of substituents other than H to the relevant positions, such as carbon or nitrogen. For example, when R 1 When it represents a single substitution, one R 1 must not be H (i.e., substituted). Similarly, when R 1 When it indicates disubstituted, the two R 1 must not be H. Similarly, when R 1 When it indicates zero or no substitution, R 1 For example, it can be hydrogen with available valences for the ring atoms, such as the carbon atoms of benzene and the nitrogen atoms in pyrrole, or simply none for ring atoms with fully saturated valences, such as the nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atoms.

[0054] As used herein, "combinations thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that a person of ordinary skill in the art can envision from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl; halogen and alkyl can be combined to form haloalkyl substituents; and halogen, alkyl and aryl can be combined to form haloaralkyl. In one example, the term substitution includes a combination of two to four listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations including up to forty atoms that are not hydrogen or deuterium, or combinations including up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will include up to twenty atoms that are not hydrogen or deuterium.

[0055] The "aza" designation in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the CH groups in the corresponding aromatic ring can be replaced by a nitrogen atom, such as, but not limited to, azatriphenylene encompassing dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the term as set forth herein.

[0056] As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be easily prepared using methods known in the art. For example, U.S. Patent No. 8,557,400, Patent Publication No. WO 2006 / 095951 and U.S. Patent Application Publication No. US2011 / 0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Review) 2007, 46, 7744-65 (which are incorporated by reference in their entirety) respectively describe the deuteration of methylene hydrogen in benzylamine and the effective way to replace aromatic ring hydrogen with deuterium.

[0057] As used herein, any specific substituents (such as but not limited to methyl, phenyl, pyridyl, etc.) include non-deuterated, partially deuterated, and fully deuterated forms thereof. Similarly, substituent classes (such as but not limited to alkyl, aryl, cycloalkyl, heteroaryl, etc.) also include non-deuterated, partially deuterated, and fully deuterated forms thereof. Chemical structures that do not further specify H or D should be considered to include non-deuterated, partially deuterated, and fully deuterated forms thereof. Some common minimal partially or fully deuterated groups are, for example, but not limited to, CD3, CD2C(CH3)3, C(CD3)3, and C6D5.

[0058] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another part, its name can be written as if it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or attaching fragments are considered equivalent.

[0059] In some cases, a pair of substituents in a molecule can be optionally joined or fused to form a ring. Preferred rings are five to nine-membered carbocyclic or heterocyclic rings, including two cases in which a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. In other cases, a pair of adjacent substituents can be optionally joined or fused to form a ring. As used herein, "adjacent" means that the two substituents involved can be adjacent to each other on the same ring, or on two adjacent rings with two closest available substitutable positions (such as 2, 2' positions in biphenyl or 1, 8 positions in naphthalene).

[0060] Layers, materials, regions, and devices may be described herein with reference to the color of light they emit. Generally, as used herein, an emissive region described as producing a particular color of light may include one or more emissive layers disposed on top of each other.

[0061] As used herein, a "red" layer, material, region, or device refers to a layer, material, region, or device that emits light in the range of about 580-700nm or whose emission spectrum in the region has the highest peak. Similarly, a "green" layer, material, region, or device refers to a layer, material, region, or device that emits or has an emission spectrum with a peak wavelength in the range of about 500-600nm; a "blue" layer, material, or device refers to a layer, material, region, or device that emits or has an emission spectrum with a peak wavelength in the range of about 400-500nm; and a "yellow" layer, material, region, or device refers to a layer, material, region, or device that has an emission spectrum with a peak wavelength in the range of about 540-600nm. In some arrangements, individual regions, layers, materials, regions, or devices can provide individual "dark blue" and "light blue" light. As used herein, in arrangements that provide individual "light blue" and "dark blue", a "dark blue" component refers to a component whose peak emission wavelength is at least about 4nm smaller than the peak emission wavelength of a "light blue" component. Typically, the "light blue" component has a peak emission wavelength in the range of about 465-500nm, and the "dark blue" component has a peak emission wavelength in the range of about 400-470nm, but these ranges may vary according to some configurations. Similarly, a color-changing layer refers to a layer that converts or adjusts light of another color into light with a wavelength as specified for the color. For example, a "red" color filter refers to a filter that produces light with a wavelength in the range of about 580-700nm. In general, there are two types of color-changing layers: color filters that adjust the spectrum by removing light of non-desired wavelengths, and color-changing layers that convert higher energy photons into lower energy. A component of "one color" refers to a component that generates or otherwise emits light of a specific color as previously described when activated or used. For example, a "first emission region of a first color" and a "second emission region of a second color different from the first color" describe two emission regions that emit two different colors as previously described when activated in the device.

[0062] As used herein, emissive materials, layers, and regions may be different from each other and from other structures based on the light that the material, layer, or region initially produces as opposed to the light that the same or different structure ultimately emits. The light initially produced is typically the result of a change in energy levels that causes the emission of photons. For example, an organic emissive material may initially produce blue light, which may be converted to red or green light by a color filter, quantum dots, or other structure, such that the complete emissive stack or sub-pixel emits red or green light. In this case, the initially emissive material or layer may be referred to as the "blue" component, even if the sub-pixel is a "red" or "green" component.

[0063] In some cases, it may be preferred to describe the color of components such as emission regions, sub-pixels, color-changing layers, etc. according to 1931 CIE coordinates. For example, a yellow emitting material may have multiple peak emission wavelengths, one in or near the edge of the "green" region and one in or near the edge of the "red" region, as previously described. Accordingly, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. Shapes in the 1931 CIE color space are constructed by tracing the trajectory between two color points and any other internal points. For example, the internal shape parameters of red, green, blue, and yellow may be defined as follows:

[0064]

[0065] More details regarding OLEDs and the above definitions can be found in US Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

[0066] As disclosed herein, an emissive layer or material, e.g. Figure 1-2 The emission layer 135 and the emission layer 220 shown in the figure, respectively, may include quantum dots. According to the understanding of those skilled in the art, unless there is a clear contrary description or the context has a contrary description, the "emission layer" or "emission material" disclosed herein may include an organic emission material and / or an emission material containing quantum dots or an equivalent structure. In general, the emission layer includes an emission material in a host matrix. Such an emission layer may only include quantum dot materials that convert light emitted by a separate emission material or other emitter, or it may also include a separate emission material or other emitter, or it itself can directly emit light by applying an electric current. Similarly, a color-changing layer, a color filter, an up-conversion or down-conversion layer or structure may include a material containing quantum dots, but such a layer may not be regarded as an "emission layer" as disclosed herein. In general, an "emission layer" or material is a layer or material that emits initial light based on an injected charge, wherein the initial light can be changed by another layer, such as a color filter or other color-changing layer that does not emit initial light in the device itself, but can re-emit light with different spectral contents based on the absorption of the initial light emitted by the emission layer and down-conversion into lower energy light emission. In some embodiments disclosed herein, the color-changing layer, color filter, up-conversion and / or down-conversion layer may be disposed outside the OLED device, for example, above or below an electrode of the OLED device.

[0067] Unless otherwise stated, any layer of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, inkjet (e.g., as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated herein by reference in their entirety), organic vapor phase deposition (OVPD) (e.g., as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated herein by reference in its entirety), and deposition by organic vapor jet printing (OVJP, also known as organic vapor jet deposition (OVJD)) (e.g., as described in U.S. Pat. No. 7,431,968, which is incorporated herein by reference in its entirety). Other suitable deposition methods include spin coating and other solution-based processes. Solution-based processes are preferably performed in a nitrogen or inert atmosphere. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (e.g., as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entirety), and patterning associated with some deposition methods such as inkjet and OVJD. Other methods may also be used. The material to be deposited may be modified to make it compatible with a particular deposition method. For example, branched or unbranched substituents (e.g., alkyl and aryl) may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 or more carbons may be used, with 3 to 20 carbons being a preferred range. The solution processability of materials having an asymmetric structure may be better than that of materials having a symmetric structure because asymmetric materials may have a lower tendency to recrystallize. Dendritic polymer substituents may be used to enhance the ability of small molecules to undergo solution processing.

[0068] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from being damaged when exposed to harmful substances in an environment including moisture, steam and / or gas, etc. The barrier layer can be deposited on a substrate, an electrode, under a substrate, an electrode, or beside a substrate, an electrode, or on any other part (including an edge) of the device. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques, and may include a composition having a single phase and a composition having multiple phases. Any suitable material or material combination may be used for the barrier layer. The barrier layer may be incorporated into an inorganic compound or an organic compound or both. A preferred barrier layer comprises a mixture of a polymer material and a non-polymer material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymer and non-polymer materials constituting the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of the polymer material relative to the non-polymer material can be in the range of 95:5 to 5:95. The polymer material and the non-polymer material can be produced from the same precursor material. In one example, the mixture of the polymer material and the non-polymer material consists essentially of polymeric silicon and inorganic silicon.

[0069] It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin-statistic limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, namely P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is produced by triplet-triplet annihilation (TTA).

[0070] On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but on the thermal population between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence must have a very small singlet-triplet gap. Thermal energy can activate the triplet state to transfer back to the singlet state. This type of delayed fluorescence is also called thermally activated delayed fluorescence (TADF). The unique feature of TADF is that the delayed component increases with increasing temperature due to increased thermal energy. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay starting from the triplet state, the fraction of the backfilled singlet excited state can potentially reach 75%. The total singlet fraction can be 100%, far exceeding the spin statistical limit of electrically generated excitons.

[0071] E-type delayed fluorescence characteristics can be found in excitation complex systems or single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires that the luminescent material has a small singlet-triplet energy gap (ΔES-T). Metal-free donor-acceptor organic light-emitting materials can achieve this. The emission of these materials is usually characterized by donor-acceptor charge transfer (CT) type emission. The spatial spacing of the HOMO and LUMO of these donor-acceptor type compounds usually causes a small ΔES-T. These states may involve CT states. Typically, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered aromatic ring containing N).

[0072] Devices made according to embodiments of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices, such as discrete light source devices or lighting panels, etc. that can be utilized by end-user product manufacturers. Such electronic component modules may optionally include driving electronics and / or power supplies. Devices made according to embodiments of the present disclosure can be incorporated into a variety of consumer products, which have one or more electronic component modules (or units). A consumer product comprising an OLED is disclosed, wherein the organic layer of the OLED includes a compound of the present disclosure. Such consumer products should include any kind of product, including one or more light sources and / or one or more visual displays of some type. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, interior or exterior lighting and / or signal lights, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cell phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, and signage. Various control mechanisms can be used to control devices manufactured according to the present disclosure, including passive matrices and active matrices. Many devices are intended to be used within a temperature range that is comfortable for humans, such as 18C to 30C, and more preferably at room temperature (20-25C), but can be used outside this temperature range (e.g., -40C to 80C).

[0073] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0074] In general terms in the art, a "sub-pixel" may refer to an emissive region in combination with any color-shifting layer, which may be a single-layer EML, a stacked device, etc., and the color-shifting layer is used to adjust the color emitted by the emissive region.

[0075] As used herein, the "emissive region" of a subpixel refers to any and all emissive layers, regions, and devices in the subpixel that are initially used to generate light. The subpixel may also include other layers stacked with the emissive region that affect the color ultimately produced by the subpixel, such as the color-changing layer disclosed herein, but such color-changing layers are typically not considered "emissive layers" as disclosed herein. A non-filtering subpixel is a subpixel that excludes a color adjustment component (e.g., a color-changing layer) but may include one or more emissive regions, layers, or devices.

[0076] In some configurations, an "emission region" may include emissive materials that emit multiple colors of light. For example, a yellow emissive region may include multiple materials that, when each material is used alone in an OLED device, emit red and green light. When used in a yellow device, the individual materials are typically not arranged so that they can be individually activated or addressed. That is, a "yellow" OLED stack containing the material cannot be driven to produce red, green, or yellow light; in fact, the stack can be driven as a whole to produce yellow light. Such an emissive region may be referred to as a yellow emissive region, although at the level of the individual emitters, the stack does not directly produce yellow light. As described in more detail below, the individual emissive materials used in the emissive region (if more than one) may be placed in the same emissive layer within the device, or in multiple emissive layers within an OLED device that includes an emissive region. As described in more detail below, embodiments disclosed herein may provide an OLED device (e.g., a display) that includes a limited number of colors of an emissive region, while including sub-pixels or other OLED devices having more colors than the number of colors of the emissive region. For example, a device as disclosed herein may include only blue and yellow emissive regions. Other colors of sub-pixels can be achieved by using a color-shifting layer (e.g., a color-shifting layer stacked with a yellow or blue emission region), or more generally, by using a color-shifting layer, an electrode, or other structure that forms a microcavity as disclosed herein, or any other suitable configuration. In some cases, the general color provided by the sub-pixel can be the same as the color provided by the emission region in the stack that defines the sub-pixel, such as where a dark blue color-shifting layer is stacked with a light blue emission region to produce a dark blue sub-pixel. Similarly, the color provided by the sub-pixel can be different from the color provided by the emission region in the stack that defines the sub-pixel, such as where a green color-shifting layer is stacked with a yellow emission region to produce a green sub-pixel.

[0077] In some configurations, an emissive region and / or emissive layer may span multiple sub-pixels, for example where fabrication of other layers and circuitry may allow portions of the emissive region or layer to be separately addressable.

[0078] An emission region as disclosed herein may be distinct from an emission "layer" as typically referred to in the art and as used herein. In some cases, a single emission region may include multiple layers, such as where a yellow emission region is made by sequentially depositing red and green emission layers to form a yellow emission region. As previously described, when such layers are present in an emission region as disclosed herein, the layers are not individually addressable within a single emission stack; in fact, the layers are activated or driven in parallel for the emission region to produce light of the desired color. In other configurations, an emission region may include a single emission layer having a single color, or multiple emission layers having the same color, in which case the color of such emission layer will be the same as the color of the emission region in which the emission layer is disposed, or will be in the same spectral interval as the color of the emission region in which the emission layer is disposed.

[0079] B. OLEDs and Devices of the Present Disclosure

[0080] In the past, the full width at half maximum (FWHM) was a common method to judge the line shape of the electroluminescent emission of a compound. However, this method does not properly correlate to the luminous efficiency at angles other than perpendicular to the viewing surface. It has been discovered that the M / T ratio can be used to analyze and quantify the luminous efficiency at angles. Narrow line shape dopants are critical to achieving high efficiency and pure color in OLED devices.

[0081] The present invention provides a method for combining an emitter with specific spectral characteristics with a device with specific optical characteristics to achieve good off-angle performance (brightness and color). In a microcavity device, as the viewing angle is shifted away from normal incidence, the effective optical thickness of the microcavity decreases, generally resulting in a reduction in the resonance between the emission spectrum of the emitter and the optical cavity, and therefore a reduction in emission intensity. This effect is made worse if the emitter is already red-shifted relative to the optical cavity resonance, as is often the case when a saturated color is desired for the device. Narrow spectrum emitters, as defined by the M / T ratio, can allow for favorable device optimization conditions to maximize off-angle brightness through appropriate device optical design.

[0082] The new M / T ratio described herein provides a better correlation between the narrowness of the metal complex and the luminescence efficiency at a certain angle. This new method effectively helps identify narrow-band emission emitters to achieve high efficiency and pure color in OLED devices.

[0083] In a first aspect, an organic electroluminescent device (OLED) is provided, comprising an anode; a cathode; and an emission region, the emission region comprising a first emission layer disposed between the anode and the cathode. The OLED further comprises a microcavity structure, and:

[0084] The first emitting layer comprises a first emitter selected from the group consisting of: a phosphorescent emitter and a fluorescent emitter;

[0085] When a voltage is applied to the OLED, the first emitting layer emits a first luminescent radiation at room temperature;

[0086] The first emission layer has a photoluminescence spectrum having a peak emission wavelength λ max , a first area T and a second area M;

[0087] where T is the total integrated area of ​​the photoluminescence spectrum, and M is in λ max -15nm and λ max The integrated area of ​​the photoluminescence spectrum between +15 nm;

[0088] The OLED has a brightness of l0 at normal incidence and a brightness of l at 60 degrees from normal incidence. 60 ;and

[0089] One of the following conditions is true:

[0090] (1) The first emitter is a phosphorescent emitter, wherein the M / T ratio is ≥ 0.38 and l 60 / l0≥15%;

[0091] (2) The first emitter is a fluorescent emitter, wherein the M / T ratio is ≥ 0.42 and l 60 / l0≥25%.

[0092] In some embodiments, the first emitter is the only emitting material in the first emitting layer. In some embodiments, one or more additional emitting materials are present in the first emitting layer.

[0093] In some embodiments, the first emitting layer is located in an optical microcavity.

[0094] To determine the M / T ratio, thin films were prepared by depositing onto a quartz substrate the same composition and thickness as used in the OLED emission region. The emission spectra of the films were measured using a Hamamatsu Quantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer with an excitation wavelength of 340 nm.

[0095] As used herein, M is the area of ​​the main peak, which is defined as the wavelength of the maximum peak (λ max )±15 nm, and T is the total area of ​​the spectrum between points where the spectral intensity is 0.1% (normalized intensity). A high M / T means that the dopant has a narrow line shape (ie, a larger portion of the emission spectrum is part of the main peak).

[0096] About brightness (l 60 and l0), the microcavity OLED was fabricated by vacuum thermal evaporation (VTE) and measured by a variable angle spectroradiometer. At a detector angle of 60 degrees to normal incidence, the luminance of the OLED is l 60 , and at a detector angle of 0 degrees (i.e., normal incidence), the brightness of the OLED is l0. 60 Divide by l0 to get l 60 / l0 value.

[0097] In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.38. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.40. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.42. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.44. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.46. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.48. In some embodiments, the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.50.

[0098] In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.42. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.44. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.46. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.48. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.50. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.52. In some embodiments, the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.54.

[0099] In some embodiments, the OLED 60 / l0 is at least 15%. In some embodiments, l 60 / l0 is at least 18%. In some embodiments, l 60 / l0 is at least 20%. In some embodiments, l 60 / l0 is at least 25%. In some embodiments, l 60 / l0 is at least 30%. In some embodiments, l 60 / l0 is at least 35%. In some embodiments, l 60 / l0 is at least 40%. In some embodiments, l 60 / l0 is at least 45%.

[0100] In some embodiments, the OLED 45 / l0 is at least 40%. In some embodiments, l 45 / l0 is at least 45%. In some embodiments, l 45 / l0 is at least 50%. In some embodiments, l 45 / l0 is at least 55%. In some embodiments, l 45 / l0 is at least 60%. In some embodiments, l 45 / l0 is at least 70%.

[0101] Similar to l 60 The measurement results, l 45 is determined by measuring the brightness of the OLED at a detector angle of 45 degrees to normal incidence. 45 Divide the value by l0 to obtain l 45 / l0 value.

[0102] In some embodiments, the OLED further comprises a hole transport layer (HTL), wherein the HTL has a peak emission wavelength λ max The HTL has a refractive index of 1.7 to 1.9. In some such embodiments, the HTL is located between the first emitting layer and the anode.

[0103] In some embodiments, each layer between the first emitting layer and the most reflective electrode is at the peak emission wavelength λ of the first emitter. max In some embodiments, each layer between the first emitting layer and the most reflective electrode has a refractive index less than 2.0 at the peak emission wavelength λ of the first emitter. max In some embodiments, each layer between the first emitting layer and the most reflective electrode has a refractive index less than 1.9 at the peak emission wavelength λ of the first emitter. max has a refractive index less than 1.8.

[0104] For the values ​​calculated herein, films of the applicable layers were deposited and the refractive indices were measured using ellipsometry.

[0105] In some embodiments, the average reflectivity of all layers between the first emitting layer and the most reflective electrode is λ at the peak emission wavelength λ of the emitter. max In some embodiments, the average reflectivity of all layers between the first emitting layer and the most reflective electrode is less than 2.0 at the peak emission wavelength λ of the first emitter. maxIn some embodiments, the average reflectivity of all layers between the first emitting layer and the most reflective electrode is less than 1.9 at the peak emission wavelength λ of the first emitter. max Less than 1.8.

[0106] In some embodiments, the most reflective electrode is the anode. In other embodiments, the most reflective electrode is the cathode.

[0107] In some embodiments, the average reflectivity of all layers between the anode and the cathode is max In some embodiments, the average reflectivity of all layers between the anode and the cathode is less than 2.0 at the peak emission wavelength λ of the first emitter. max In some embodiments, the average reflectivity of all layers between the anode and the cathode is less than 1.9 at the peak emission wavelength λ of the first emitter. max Less than 1.8.

[0108] In some embodiments, the OLED includes a hole transport layer (HTL), wherein the HTL has a peak emission wavelength λ of the first emitter. max The material has a refractive index of at least 2.0.

[0109] In some embodiments, at least one layer between the first emitting layer and the most reflective electrode is at the peak emission wavelength λ of the emitter. max The material has a refractive index of at least 2.0.

[0110] In some embodiments, the average reflectivity of all layers between the first emitting layer and the most reflective electrode is λ at the peak emission wavelength λ of the emitter. max The minimum score is 2.0.

[0111] In some embodiments, the average reflectivity of all layers between the anode and the cathode is max The minimum score is 2.0.

[0112] In some embodiments, the most reflective electrode is the anode. In some embodiments, the most reflective electrode is the cathode.

[0113] In some embodiments, the OLED 60 / l0 is at least 20%. In some embodiments, l 60 / l0 is at least 25%. In some embodiments, l 60 / l0 is at least 30%. In some embodiments, l 60 / l0 is at least 35%. In some embodiments, l 60 / l0 is at least 40%. In some embodiments, l 60 / l0 is at least 45%. In some embodiments, l 60 / l0 is at least 40%. In some embodiments, l 60 / l0 is at least 45%. In some embodiments, l 60 / l0 is at least 50%. In some embodiments, l 60 / l0 is at least 55%. In some embodiments, l 60 / l0 is at least 60%. In some embodiments, l 60 / l0 is at least 70%.

[0114] In some embodiments, the OLED further comprises a cover layer disposed over an upper portion of the anode or the cathode. In some embodiments, the cover layer is over or deposited on the cathode. In some embodiments, the cathode is between the cover layer and the anode.

[0115] In some embodiments, the thickness of the cover layer is greater than 50 nm. In some embodiments, the thickness of the cover layer is greater than 60 nm. In some embodiments, the thickness of the cover layer is greater than 70 nm.

[0116] In some embodiments, the cover layer is at a peak emission wavelength λ of the first emitter. max In some embodiments, the cover layer has a refractive index in the range of 1.7 to 1.9 at the peak emission wavelength λ of the first emitter. max In some embodiments, the cover layer has a refractive index of at least 1.9 at the peak emission wavelength λ of the first emitter. max The material has a refractive index of at least 2.0.

[0117] In some embodiments, in the absence of an outcoupling structure, the OLED satisfies at least one of the conditions (1) or (2).

[0118] In some embodiments, the OLED further comprises an outcoupling structure. In some embodiments, the outcoupling structure is selected from a lens, a microlens, a scattering medium, a grating, and a periodic structure.

[0119] In some embodiments, the outcoupling structure satisfies condition (1) or condition (2).

[0120] In some embodiments including an outcoupling structure, the OLED will still satisfy at least one of condition (1) or condition (2) without the outcoupling structure.

[0121] In some embodiments, the first emitting layer is located at a first antinode of the optical microcavity. As used herein, the first antinode is a distance λ above the bottom of the optical microcavity. max / 4±15%.

[0122] In some embodiments, the first emitting layer is located at a second antinode of the optical microcavity. In some embodiments, the first emitting layer is located at a third or higher antinode of the optical microcavity.

[0123] In some embodiments, the first emitter is the only emissive compound in the first emissive layer.

[0124] In some embodiments, at normal incidence, the first emitter contributes at least 50% of the total brightness of the first luminescent radiation emitted by the OLED.This determination can be made using photoluminescence measurements.

[0125] In some embodiments, at normal incidence, the first emitter contributes at least 60% of the luminescence of the first luminescent radiation. In some embodiments, at normal incidence, the first emitter contributes at least 70% of the intensity of the first luminescent radiation. In some embodiments, at normal incidence, the first emitter contributes at least 80% of the intensity of the first luminescent radiation. In some embodiments, at normal incidence, the first emitter contributes at least 90% of the intensity of the first luminescent radiation. In some embodiments, at normal incidence, the first emitter contributes at least 95% of the intensity of the first luminescent radiation.

[0126] In some embodiments, the first luminescent radiation is green or yellow, wherein the 1931 CIEx range is 0.15 to 0.45. In some embodiments, the first luminescent radiation is green (500-600 nm).

[0127] In some embodiments, the first luminescent radiation is blue, wherein the 1931 CIEy range is 0.005 to 0.35. In some embodiments, the first luminescent radiation is blue (400-500 nm).

[0128] In some embodiments, the first luminescent radiation is red, wherein the CIE range is 0.60 to 0.75. In some embodiments, the first luminescent radiation is red (600-700 nm).

[0129] In some embodiments, the first emitter is an emitter having phosphorescent capabilities.

[0130] In some embodiments, the first emitter is capable of emitting light from a triplet excited state to a singlet ground state in an OLED at room temperature. In some such embodiments, the first emitter emits blue light (400-500 nm). In some embodiments, the first emitter emits red light (600-700 nm). In other embodiments, the first emitter emits green light (500-600 nm).

[0131] In some embodiments, the first emitter is a metal coordination complex having a metal-carbon bond.

[0132] In some embodiments, the first emitter is a metal coordination complex having a metal-nitrogen bond.

[0133] In some embodiments, the first emitter is a metal coordination complex having a metal-oxygen bond.

[0134] In some embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt.

[0135] In some embodiments, the first emitter has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0136] Where L 1 , L 2 and L 3 Can be the same or different;

[0137] where x is 1, 2, or 3;

[0138] Where y is 0, 1 or 2;

[0139] where z is 0, 1 or 2;

[0140] Where x+y+z is the oxidation state of metal M;

[0141] Where L 1 Select from the group consisting of the structures in Listing 1 below:

[0142]

[0143]

[0144] Where L 2 and L 3 Independently choose freedom and the group consisting of the structures in Listing 1 as defined in this document;

[0145] in:

[0146] T is selected from the group consisting of B, Al, Ga and In;

[0147] K 1 ' is a direct key or selected from NR e , PR e , O, S and Se;

[0148] Each Y 1 To Y 13 independently selected from the group consisting of carbon and nitrogen;

[0149] Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;

[0150] R e and R f may be fused or joined to form a ring;

[0151] Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

[0152] Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0153] R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two adjacent substituents of may be fused or joined to form a ring or to form a multidentate ligand.

[0154] In some embodiments, L 1 You can select from the group consisting of the following structures in Listing 1a:

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162] in:

[0163] T is selected from the group consisting of B, Al, Ga and In;

[0164] W 1 Selected from the group consisting of direct bond, BR, NR, PR, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CRR', P(O)R, SiRR' and GeRR';

[0165] W 2 is B, N, P, CR, SiR or GeR;

[0166] K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ;

[0167] Y 1 To Y 18 Each of is independently selected from the group consisting of C and N;

[0168] Y a Each of ', Y' and Y" is independently selected from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CRe R f 、SiR e R f and GeR e R f ;

[0169] Each R a' , R b' , R c' and R d' independently represents monosubstitution to the maximum allowed number of substitutions or no substitution;

[0170] R, R', R a1 , R b1 , R c1 , R d1 , R a' , R b' , R c' , R d' , R e and R f each of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0171] R, R', R a1 , R b1 , R c1 , R d1 , R a' , R b' , R c' , R d' , R e and R f Any two substituents of may be fused or joined to form a ring or to form a polydentate ligand.

[0172] In some embodiments, L 2 and L 3 Each independently selected from the group consisting of the structures in Listing 1b below:

[0173]

[0174]

[0175]

[0176] in:

[0177] T is selected from the group consisting of B, Al, Ga and In;

[0178] K 1 'Selected from the group consisting of: single bond, O, S, NR e , PR e , BR e , CR e R f and SiR e R f ;

[0179] Y 1 To Y 13 Each of is independently selected from the group consisting of C and N;

[0180] Y'Select from the group consisting of: BR e , BR e R f NR e , PR e 、P(O)R e ,O,S,Se,C=O,C=S,C=Se,C=NR e 、C=CR e R f 、S=O、SO2、CR e R f 、SiR e R f and GeR e R f ;

[0181] R e and R f may be fused or joined to form a ring;

[0182] Each R a , R b , R c and R d independently represent mono-substitution to the maximum allowed number of substitutions, or no substitution;

[0183] R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R feach of which is independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0184] R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two substituents of may be fused or joined to form a ring or to form a polydentate ligand.

[0185] In some embodiments, L 2 and L 3 Each independently selected from the group consisting of the structures in Listing 1c below:

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] in:

[0194] R a' , R b' , R c' , R d' and R e' Each independently represents zero substitution, monosubstitution, or up to the maximum allowed number of substitutions on its associated ring;

[0195] R a' , R b' , R c' , R d' and R e'are each independently hydrogen or a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

[0196] R a' , R b' , R c' , R d' and R e' The two substituents may be fused or joined to form a ring or to form a polydentate ligand.

[0197] In some embodiments, L 2 Include In some embodiments, Y 1 To Y 4 In some embodiments, each of Y is independently carbon. 1 To Y 4 At least one of is N. In some embodiments, Y 1 To Y 4 Exactly one of is N. In some embodiments, Y 1 is N. In some embodiments, Y 2 is N. In some embodiments, Y 3 is N. In some embodiments, Y 4 is N. In some embodiments, R a At least one of R is a tertiary alkyl, a silane group or a germyl group. a In some embodiments, at least one of Y 3 is C, and the R connected to it a is a tertiary alkyl group, a silane group or a germanium group. 1 To Y 3 It's C, Y 4 is N, and with Y 3 Connected R a is a tertiary alkyl group, a silane group or a germanium group. 1 To Y 3 It's C, Y 4 is N, and with Y 2 Connected R a is a tertiary alkyl group, a silane group or a germanium group. b At least one of R is a tertiary alkyl, a silane group, or a germyl group. In some embodiments, the tertiary alkyl group is a tert-butyl group. In some embodiments, at least one pair of R a , a pair of Rb or a pair of R a and R b Join or condense into a ring.

[0198] In some embodiments, the first emitter has a formula selected from the group consisting of: Ir(L 1 )3、Ir(L 1 )(L 2 )2、Ir(L 1 )2(L 2 )、Ir(L 1 )2(L 3 )、Ir(L 1 )(L 2 )(L 3 ) and Pt(L 1 )(L 2 );

[0199] Where L 1 , L 2 and L 3 are different from each other in the Ir compounds;

[0200] Where L 1 and L 2 may be the same or different in the Pt compound; and

[0201] Where L 1 and L 2 may be linked to form a tetradentate ligand in the Pt compound.

[0202] In some embodiments, the first emitter is selected from the group consisting of the structures in Listing 2 below:

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214] in:

[0215] X 96 To X 99 Each of is independently C or N;

[0216] Y 100 and Y 200 Each of which is independently selected from the group consisting of NR, O, S and Se;

[0217] L is independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0218] X 100 at each occurrence selected from the group consisting of: O, S, Se, NR", and CRR';

[0219] Each R 10a , R 20a , R 30a , R 40a , R 50a , R A" , R B" , R C" , R D" , R E" and R F" independently represents a single substitution up to the maximum number of substitutions, or no substitution;

[0220] Each R, R', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、RF ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0221] With respect to the foregoing compounds, it is understood that for each of the compounds having a Pt center, the Pt atom may be replaced by a Pd atom, and it is intended to specifically describe those Pd derivatives as well.

[0222] In some embodiments, L 2 Choose from L Bk A group consisting of, wherein k is an integer from 1 to 621, and L B1 To L B621 Each of them is defined in Listing 3 below:

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245] In some embodiments, the first emitter is a fluorescent emitter. In some embodiments, the first emitter is a delayed fluorescent compound that acts as a thermally activated delayed fluorescence (TADF) emitter in an OLED at room temperature. In some embodiments, the TADF emitter comprises at least one donor group and at least one acceptor group.

[0246] In some embodiments, the TADF emitter is a metal complex. In some embodiments, the TADF emitter is a Cu, Ag, or Au complex. In some embodiments, the TADF emitter is a non-metal complex.

[0247] In some embodiments, the first emitter is a molecule having the formula M(L) as defined herein. 5 )(L 6 )'s TADF emitter.

[0248] In some embodiments, the first emitter is a TADF emitter selected from the group consisting of the structures in List 5 defined herein.

[0249] In some embodiments, the first emitter is a TADF emitter comprising at least one chemical moiety selected from the group consisting of the structures in List 6 as defined herein.

[0250] In some embodiments where the first emitter is a TADF emitter as described above, any carbon ring atoms (up to a total maximum of three) in each benzene ring of any of the above structures along with their substituents may be replaced by N.

[0251] In some embodiments in which the first emitter is a TADF emitter as described above, the TADF emitter comprises at least one chemical moiety selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole and oxadiazole.

[0252] In some embodiments where the first emitter is a TADF emitter as described above, the first emitting layer further comprises a sensitizer (S1), and the first emitter is an acceptor that is a fluorescent emitter.

[0253] In some embodiments, the fluorescent emitter comprises at least one chemical moiety selected from the group consisting of the structures in List 7 as defined herein.

[0254] In some embodiments comprising portions of Listing 7, any carbon ring atoms (up to a total maximum of three) in each benzene ring of any of the above structures, along with their substituents, can be replaced by N.

[0255] In some embodiments, the fluorescent emitter is selected from the group consisting of the structures in List 8 as defined herein.

[0256] In some embodiments, the fluorescent emitter is selected from the group consisting of structures in the list of acceptors defined herein.

[0257] In some embodiments, the sensitizer (S1) is capable of acting as a phosphorescent emitter in an OLED at room temperature. In some embodiments, the sensitizer (S1) is a metal coordination complex having at least one of a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond.

[0258] In some embodiments, the sensitizer (S1) is a metal coordination complex. The metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au and Cu. In some such embodiments, the metal is Ir. In other embodiments, the metal is Pt.

[0259] In some embodiments, the sensitizer (S1) has the formula M(L A ) x (L B ) y (L C ) z ;

[0260] Where L A , L B and L C Can be the same or different;

[0261] where x is 1, 2, or 3;

[0262] Where y is 0, 1 or 2;

[0263] where z is 0, 1 or 2;

[0264] Where x+y+z is the oxidation state of metal M;

[0265] Where L A Selected from the group consisting of the structures in Listing 1 as defined herein;

[0266] Where L B and L C Independently choose freedom and the structure in Listing 1; where:

[0267] T is selected from the group consisting of B, Al, Ga and In;

[0268] K 1 ' is a direct key or selected from NR e , PR e , O, S and Se;

[0269] Each Y 1 To Y 13 independently selected from the group consisting of carbon and nitrogen;

[0270] Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;

[0271] R e and R f may be fused or joined to form a ring;

[0272] Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

[0273] Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c, R d , R e and R f is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0274] Where R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two of the may be fused or joined to form a ring or to form a multidentate ligand.

[0275] In some embodiments, the metal is selected from the group consisting of Cu, Ag, or Au.

[0276] In some embodiments, the sensitizer (S1) has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C )、Ir(L A )(L B )(L C ) and Pt(L A )(L B );

[0277] Where L A , L B and L C are different from each other in the Ir compounds;

[0278] Where L A and L B may be the same or different in the Pt compound; and

[0279] Where L A and L B may be linked to form a tetradentate ligand in the Pt compound.

[0280] In some embodiments, the sensitizer (S1) is selected from the group consisting of compounds in List 2 as defined herein;

[0281] in:

[0282] X 96 To X 99 Each of is independently C or N;

[0283] Each Y 100 independently selected from the group consisting of NR, O, S and Se;

[0284] L is independently selected from the group consisting of a direct bond, BR, BRR', NR, PR, O, S, Se, C=O, C=S, C=Se, C=NR, C=CRR', S=O, SO2, CR, CRR', SiRR', GeRR', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0285] X 100 at each occurrence selected from the group consisting of: O, S, Se, NR, and CRR';

[0286] Each R 10a , R 20a , R 30a , R 40a and R 50a , R A ”、R B ”、R C ”、R D ”、R E ” and R F " independently means mono-substitution up to a maximum of multiple substitutions or no substitution; and

[0287] R, R', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、R F ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0288] In some embodiments, the sensitizer (S1) is selected from the group consisting of the structures in List 2 as defined herein, wherein R, R', R", R'", R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、R F ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " includes a moiety selected from the group consisting of fully or partially deuterated aryl, fully or partially deuterated alkyl, borane, silane, germane, 2,6-terphenyl, 2-biphenyl, 2-(tert-butyl)phenyl, tetraphenylene, tetralin, and combinations thereof.

[0289] In some embodiments, the first emissive layer further comprises a host, wherein the host comprises a triphenylene containing a benzo-fused thiophene or a benzo-fused furan;

[0290] wherein any substituent in the subject is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 、OAr1、N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar1、Ar1-Ar2、C n H 2n -Ar1, or no substituent;

[0291] wherein n is 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and heteroaromatic analogs thereof.

[0292] In some embodiments, the first emissive layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, azaborane, oxaborabine, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0293] In some embodiments, the first emissive layer further comprises a host, wherein the host is selected from the group consisting of Host Group 1 defined herein.

[0294] In some embodiments, the first emissive layer further comprises a host, wherein the host comprises a metal complex.

[0295] In some embodiments, the OLED of the present disclosure comprises an emission region disposed between an anode and a cathode; wherein the emission region comprises a sensitizer compound and an acceptor compound; wherein the sensitizer transfers energy to an acceptor compound as an emitter. In some embodiments, the sensitizer compound is capable of emitting light from a triplet excited state to a singlet ground state in an OLED at room temperature. In some embodiments, the sensitizer compound is capable of acting as a phosphorescent emitter, a TADF emitter, or a doublet emitter in an OLED at room temperature. In some embodiments, the acceptor compound is selected from the group consisting of: a delayed fluorescent compound that acts as a TADF emitter in an OLED at room temperature, a fluorescent compound that acts as a fluorescent emitter in an OLED at room temperature. In some embodiments, the fluorescent emitter may be a singlet or doublet emitter. In some such embodiments, the singlet emitter may also include a TADF emitter, and in addition, a multi-resonance MR-TADF emitter. As used herein, a description of delayed fluorescence may be found in paragraphs 0083-0084 of U.S. Application Publication US20200373510A1, the entire contents of which are incorporated herein by reference.

[0296] In some embodiments of OLEDs, the sensitizer and acceptor compound are present in separate layers within the emissive region.

[0297] In some embodiments, the sensitizer and the receptor compound are present in one or more layers in the emission region as a mixture. It should be understood that the mixture in a given layer may be a homogeneous mixture, or the compounds in the mixture may have a concentration gradient throughout the thickness of a given layer. The concentration gradient may be linear, nonlinear, sinusoidal, etc. When there is more than one layer in the emission region having a mixture of a sensitizer and a receptor compound, the type of mixture (i.e., homogeneous or gradient concentration) and the concentration level of the compound in the mixture in each layer of more than one layer may be the same or different. In addition to the sensitizer and the receptor compound, one or more other functional compounds may also be present, such as but not limited to the main body also mixed into the mixture.

[0298] In some embodiments, the receptor compound may be present in two or more layers with the same or different concentrations. In some embodiments, when two or more layers contain receptor compounds, the concentration of the receptor compound in at least two of the two or more layers is different. In some embodiments, the concentration of the sensitizer compound in the layer containing the sensitizer compound is in the range of 1 to 50 wt%, 10 to 20 wt%, or 12 to 15 wt%. In some embodiments, the concentration of the receptor compound in the layer containing the receptor compound is in the range of 0.1 to 10 wt%, 0.5 to 5 wt%, or 1 to 3 wt%.

[0299] In some embodiments, the emission region contains N layers, where N>2. In some embodiments, the sensitizer compound is present in each of the N layers, and the receptor compound is contained in less than or equal to N-1 layers. In some embodiments, the sensitizer compound is present in each of the N layers, and the receptor compound is contained in less than or equal to N / 2 layers. In some embodiments, the receptor compound is present in each of the N layers, and the sensitizer compound is contained in less than or equal to N-1 layers. In some embodiments, the receptor compound is present in each of the N layers, and the sensitizer compound is contained in less than or equal to N / 2 layers.

[0300] In some embodiments, when a voltage is applied across the OLED, the OLED emits luminescent emission that includes an emission component from the S1 energy (first singlet energy) of the acceptor compound. In some embodiments, at least 65%, 75%, 85%, or 95% of the emission of the OLED is emitted by the acceptor compound at a wavelength of at least 10 cd / m 2 In some embodiments, the S1 energy of the acceptor compound is lower than the S1 energy of the sensitizer compound.

[0301] In some embodiments, the T1 energy (first triplet energy) of the host compound is greater than or equal to the T1 energy of the sensitizer compound and the receptor compound, and the T1 energy of the sensitizer compound is greater than or equal to the S1 energy (first singlet energy) of the receptor compound. In some embodiments, the S1-T1 energy gap of the sensitizer compound and / or the receptor compound and / or the first host compound and / or the second host compound is less than 400, 300, 250, 200, 150, 100, or 50 meV. In some embodiments, the absolute energy difference between the HOMO of the sensitizer compound and the HOMO of the receptor compound is less than 0.6, 0.5, 0.4, 0.3, or 0.2 eV. In some embodiments, the absolute energy difference between the LUMO of the sensitizer compound and the LUMO of the receptor compound is less than 0.6, 0.5, 0.4, 0.3, or 0.2 eV.

[0302] In some embodiments where the sensitizer compound provides monochromatic sensitization (ie, minimal energy loss after energy transfer to the acceptor compound), the acceptor compound has a Stokes shift of 30, 25, 20, 15, or 10 nm or less. Examples are broad blue phosphors that are sensitive to narrow blue emitting acceptors.

[0303] In some embodiments where the sensitizer compound provides a down conversion process (eg, a blue emitter for sensitizing a green emitter, or a green emitter for sensitizing a red emitter), the acceptor compound has a Stokes shift of 30, 40, 60, 80, or 100 nm or more.

[0304] In some embodiments, the difference between the λmax of the emission spectrum of Compound S1 and the λmax of the absorption spectrum of Compound A1 is 50, 40, 30 or 20 nm or less. In some embodiments, the light absorption area of ​​Compound A1 overlaps the spectrum of the light emitting area of ​​Compound S1 by more than 5%, 10%, 15%, 20%, 30%, 40%, 50% or more relative to the light emitting area of ​​Compound S1.

[0305] One way to quantify the qualitative relationship between a sensitizer compound (a compound to be used as a sensitizer in the emissive region of an OLED of the present disclosure) and an acceptor compound (a compound to be used as an acceptor in the emissive region of an OLED of the present disclosure) is to determine the value Δλ=λ max1 -λ max2 , where λ max1 and λ max2 The definition is as follows. max1 is the emission maximum of the sensitizer compound at room temperature when the sensitizer compound is used as the only emitter in a first monochrome OLED (an OLED emitting only one color) having a first host. max2 is the emission maximum of the acceptor compound at room temperature when the acceptor compound is used as the only emitter in a second monochrome OLED having the same first host.

[0306] In some embodiments of the disclosed OLEDs where the sensitizer compound provides monochromatic sensitization (i.e., minimal energy loss upon energy transfer to the acceptor compound), Δλ (measured as described above) is equal to or less than a number selected from the group consisting of: 15, 12, 10, 8, 6, 4, 2, 0, -2, -4, -6, -8, and -10 nm.

[0307] In some embodiments, the spectral overlap integral of Compound A1 and Compound S1 is at least 10 14 nm 4* L / cm*mol. In some embodiments, the spectral overlap integral of Compound A1 and Compound S1 is at least 5 x 10 14 nm 4* L / cm*mol. In some embodiments, the spectral overlap integral of Compound A1 and Compound S1 is at least 10 15 nm 4* L / cm*mol.

[0308] As used herein, "spectral overlap integral" is determined by multiplying the extinction spectrum of Compound A1 by the emission spectrum of Compound S1 normalized to the area under the curve. The higher the spectral overlap, the more Forster The better the resonance energy transfer (FRET) efficiency. The FRET ratio is proportional to the spectral overlap integral. Therefore, high spectral overlap can help improve FRET efficiency and shorten the exciton lifetime in OLEDs.

[0309] In some embodiments, Compound A1 and Compound S1 are selected to increase spectral overlap. The increase in spectral overlap can be achieved in several ways, such as increasing the oscillation intensity of Compound A1, minimizing the distance between the peak emission intensity of Compound S1 and the absorption peak of Compound A1, and narrowing the linear shape of the emission of Compound S1 or the absorption of Compound A1. In some embodiments, the oscillation intensity of Compound A1 is greater than or equal to 0.1.

[0310] In some embodiments where the acceptor emission is red-shifted by sensitization, the absolute value of Δλ is equal to or greater than a value selected from the group consisting of 20, 30, 40, 60, 80, 100 nm.

[0311] In an embodiment, the sensitizer compound is capable of acting as a phosphorescent emitter in an OLED at room temperature, and the sensitizer compound may be a metal coordination complex having a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond. In some embodiments, the metal is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Zr, Au, Ag, and Cu. In some embodiments, the metal is Ir. In some embodiments, the metal is Pt. In some embodiments, the sensitizer compound has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ;

[0312] Where L 1 , L 2 and L 3 Can be the same or different;

[0313] where x is 1, 2, or 3;

[0314] Where y is 0, 1 or 2;

[0315] where z is 0, 1 or 2;

[0316] Where x+y+z is the oxidation state of metal M;

[0317] Where L 1 Selected from the group consisting of structures in the following ligand list:

[0318]

[0319]

[0320]

[0321] Where L 2 and L 3 Independently selected from the group consisting of: and a structure from the ligand list; where:

[0322] T is selected from the group consisting of B, Al, Ga and In;

[0323] K 1 ' is a direct key or selected from NR e , PR e , O, S and Se;

[0324] Each Y 1 To Y 13 independently selected from the group consisting of carbon and nitrogen;

[0325] Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ;

[0326] R e With R f may be fused or joined to form a ring;

[0327] Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution;

[0328] Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; and

[0329] Where R a1 , R b1 , R c1 , R d1, R a , R b , R c and R d Any two of may be fused or joined to form a ring or to form a multidentate ligand.

[0330] In some embodiments, Formula M (L 1 ) x (L 2 ) y (L 3 ) z The metal in is selected from the group consisting of Cu, Ag or Au.

[0331] In some embodiments of OLEDs, the sensitizer compound has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C )、Ir(L A )(L B )(L C ) and Pt(L A )(L B );

[0332] Where L A , L B and L C They are different from each other in Ir compounds;

[0333] Where L A and L B may be the same or different in the Pt compound; and

[0334] Where L A and L B Can be linked to form a tetradentate ligand in the Pt compound.

[0335] In some embodiments of OLEDs, the sensitizer compound is selected from the group consisting of compounds in the following list of sensitizers:

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345] X 96 To X 99 Each of is independently C or N;

[0346] Each Y 100 Independently selected from the group consisting of NR", O, S and Se;

[0347] L is independently selected from the group consisting of a direct bond, BR", BR"R'", NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR", C=CR"R'", S=O, SO2, CR", CR"R'", SiR"R'", GeR"R'", alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0348] X 100 and X 200 is independently selected at each occurrence from the group consisting of O, S, Se, NR", and CR"R'";

[0349] Each R 10a , R 20a , R 30a , R 40a and R 50a , R A "、R B" , R C" , R D" , R E" and R F" independently represents mono- to maximal substitution, or no substitution;

[0350] R, R', R", R'', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2'、R A" , R B" , R C" , R D" , R E" , R F" , R G" , R H" , R I" , R J" , R K" , R L" , R M" and R N" Each of is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; wherein any two substituents may be fused or joined to form a ring.

[0351] In some embodiments of the OLED wherein the sensitizer is selected from the group consisting of structures in the list of sensitizers, R, R', R", R'", R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、R F ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " includes a moiety selected from the group consisting of fully or partially deuterated aryl, fully or partially deuterated alkyl, borane, silane, germane, 2,6-terphenyl, 2-biphenyl, 2-(tert-butyl)phenyl, tetraphenylene, tetralin, and combinations thereof.

[0352] It is to be understood that the metallic Pt in each of those compounds in the list of sensitizers may be replaced by Pd, and those derived Pd compounds are also intended to be specifically covered.

[0353] In some embodiments, the phosphorescent material or sensitizer may be selected from the group consisting of:

[0354]

[0355]

[0356]

[0357]

[0358] In some embodiments, the sensitizer and / or the acceptor may be a phosphorescent or fluorescent emitter. Phosphorescence generally refers to the emission of photons when the electron spin changes, that is, the initial and final states of the emission have different magnifications, such as from the T1 to the S0 state. The Ir and Pt complexes currently widely used in OLEDs belong to the family of phosphorescent emitters. In some embodiments, if the excited complex formation involves a triplet emitter, such excited complexes may also emit phosphorescence. On the other hand, a fluorescent emitter generally refers to the emission of photons with unchanged electron spin, such as from the S1 to the S0 state. A fluorescent emitter may be a delayed fluorescent emitter or a non-delayed fluorescent emitter. Depending on the spin state, a fluorescent emitter may be a singlet emitter or a doublet emitter or other multiplet emitter. It is believed that the internal quantum efficiency (IQE) of a fluorescent OLED can exceed the 25% spin statistical limit through delayed fluorescence. There are two types of delayed fluorescence, namely P-type and E-type delayed fluorescence. P-type delayed fluorescence is produced by triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplet states, but on the thermal population between the triplet state and the singlet excited state. Thermal energy can activate the triplet state to transfer back to the singlet state. This type of delayed fluorescence is also called thermally activated delayed fluorescence (TADF). E-type delayed fluorescence characteristics can be found in exciplex systems or single compounds. Without being bound by theory, it is believed that TADF requires the compound or exciplex to have a small singlet-triplet energy gap (ΔE) of less than or equal to 300 meV. S-T), and in some preferred embodiments, less than or equal to 250, 200, 150, 100 or 50 meV. There are two main types of TADF emitters, one is called donor-acceptor type TADF and the other is called multi-resonance (MR) type TADF. Typically, a donor-acceptor single compound is constructed by connecting an electron donor portion (e.g., an amino or carbazole derivative) and an electron acceptor portion (e.g., a six-membered aromatic ring containing N). A donor-acceptor excited complex can be formed between a hole transport compound and an electron transport compound. Examples of MR-TADF include highly conjugated boron-containing compounds. In some embodiments, the reverse intersystem crossing time duration of delayed fluorescence emission from T1 to S1 at 293K is less than or equal to 10 microseconds. In some embodiments, such a time duration may be greater than 10 microseconds and less than 100 microseconds.

[0359] In some embodiments of the OLED, at least one of the following conditions is true:

[0360] (1) The sensitizer compound can act as a TADF emitter in OLED at room temperature;

[0361] (2) The acceptor compound is a delayed fluorescent compound that acts as a TADF emitter in OLEDs at room temperature.

[0362] In some embodiments of the OLED, the TADF emitter comprises at least one donor group and at least one acceptor group. In some embodiments, the TADF emitter is a metal complex. In some embodiments, the TADF emitter is a non-metal complex. In some embodiments, the TADF emitter is a Cu, Ag, or Au complex.

[0363] In some embodiments of OLEDs, the TADF emitter has the formula M(L 5 )(L 6 ), where M is Cu, Ag or Au, L 5 and L 6 Different, and L 5 and L 6 Independently selected from the group consisting of the structures in Listing 4 below:

[0364]

[0365]

[0366] Among them A 1 -A 9 are each independently selected from C or N;

[0367] Each R P , R P , R U, R SA , R SB , R RA , R RB , R RC , R RD , R RE and R RF are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof.

[0368] In some embodiments of OLEDs, the TADF emitter may be one of the following:

[0369]

[0370] Each R A ”、R B ”、R C ”、R D ”、R E ” and R F " may independently represent a single to the maximum possible number of substitutions, or no substitution;

[0371] Each R”, R”', R A1 , R A ”、R B ”、R C ”、R D ”、R E ” and R F " is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein; wherein any two substituents may be fused or joined to form a ring.

[0372] wherein L is independently selected from the group consisting of a direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR", C=CR"R"', S=O, SO2, CR", CR"R"', SiR"R"', GeR"R"', alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

[0373] wherein each of L1' and L2' is a monodentate anionic ligand,

[0374] wherein each of X1′ and X2′ is a halogen group; and wherein any two substituents may be fused or joined to form a ring.

[0375] In some embodiments of the OLED, the TADF emitter is selected from the group consisting of the structures in List 5 below:

[0376]

[0377]

[0378]

[0379] In some embodiments of the OLED, the TADF emitter comprises a boron atom. In some embodiments of the OLED, the TADF emitter comprises at least one chemical moiety selected from the group consisting of the structures in Listing 6 below:

[0380]

[0381] where Y T , Y U , Y V and Y W Each independently selected from the group consisting of BR, NR, PR, O, S, Se, C=O, S=O, SO2, BRR', CRR', SiRR' and GeRR';

[0382] Each R T can be the same or different, and each R T is independently a donor, an acceptor group, an organic linker bonded to a donor, an organic linker bonded to an acceptor group, or a terminal group selected from the group consisting of an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aralkyl group, an aryl group, a heteroaryl group, and combinations thereof; and

[0383] R and R' are each independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0384] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures up to a total of up to three carbon ring atoms together with their substituents can be replaced by N.

[0385] In some embodiments, the TADF emitter comprises at least one chemical moiety selected from the group consisting of nitrile, isonitrile, borane, fluoro, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moiety and the donor moiety as described herein can be directly linked, linked via a conjugated linking group or a non-conjugated linking group (e.g., sp3 carbon or silicon atom).

[0386] In some embodiments, the acceptor is a fluorescent compound that acts as an emitter in an OLED at room temperature. In some embodiments, the fluorescent compound comprises at least one chemical moiety selected from the group consisting of the structures in Listing 7 below:

[0387]

[0388]

[0389]

[0390] where Y F , Y G , Y H and Y I Each of which is independently selected from the group consisting of: BR, NR, PR, O, S, Se, C=O, S=O, SO2, BRR', CRR', SiRR' and GeRR';

[0391] Where X F and X G are each independently selected from the group consisting of C and N; and

[0392] Each R F , R G , R and R' are independently hydrogen or a substituent selected from the group consisting of general substituents defined herein.

[0393] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures up to a total of up to three carbon ring atoms together with their substituents can be replaced by N.

[0394] In some embodiments of the OLED, the fluorescent compound is selected from the group consisting of the structures in Listing 8 below:

[0395]

[0396]

[0397]

[0398]

[0399] where Y F1 To Y F4 Each independently selected from O, S and NR F1 ;

[0400] Where R F1 and R 1S To R 9SEach independently represents a single substitution to the maximum possible number of substitutions or no substitution; and

[0401] Where R F1 and R 1S To R 9S Each is independently hydrogen or a substituent selected from the group consisting of general substituents as defined herein.

[0402] In some embodiments, the receptor compound is selected from the group consisting of the structures in the following receptor list:

[0403]

[0404]

[0405]

[0406]

[0407]

[0408]

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417]

[0418]

[0419]

[0420]

[0421]

[0422]

[0423]

[0424]

[0425]

[0426]

[0427]

[0428] Aza-substituted variants thereof, fully or partially deuterated variants thereof, and combinations thereof.

[0429] In some of the above embodiments, any carbon ring atom in each benzene ring of any of the above structures up to a total of up to three carbon ring atoms together with their substituents can be replaced by N.

[0430] In some embodiments, the acceptor compound comprises a fused ring system having at least five to fifteen 5-membered and / or 6-membered aromatic rings. In some embodiments, the acceptor compound has a first group and a second group, wherein the first group and the second group do not overlap; wherein at least 80% of the singlet excited state population of the lowest singlet excited state is localized in the first group; and wherein at least 80%, 85%, 90%, or 95% of the triplet excited state population of the lowest triplet excited state is localized in the second group.

[0431] In some embodiments, the emission region further comprises a first host. In some embodiments, the sensitizer compound forms an excitation complex with the first host in the OLED at room temperature. In some embodiments, the LUMO energy of the first host is lower than the LUMO energy of the sensitizer compound and the receptor compound in the emission region. In some embodiments, the HOMO energy of the first host is lower than the HOMO energy of the sensitizer compound and the receptor compound in the emission region. In some embodiments, the HOMO energy of the first host is higher than the HOMO energy of the sensitizer compound and the receptor compound in the emission region. In some embodiments, the HOMO energy of the first host is higher than the HOMO energy of at least one of the sensitizer compound and the receptor compound in the emission region.

[0432] In some embodiments, the emission region further comprises a second host. In some embodiments, the first host forms an excitation complex with the second host in the OLED at room temperature. In some embodiments, the S1-T1 energy gap in the excitation complex formed by the first host and the second host is less than 0.4, 0.3, 0.2 or 0.1 eV. In some embodiments, the T1 energy of the excitation complex is greater than 2.5, 2.6, 2.7 or 2.8 eV. In some embodiments, the concentration of the first and second hosts in one or more layers containing the first and second hosts is greater than the concentration of the sensitizer compound and the receptor compound in one or more layers containing the sensitizer compound and the receptor compound. In some embodiments, the concentration of the first and second hosts in one or more layers containing the first and second hosts is greater than the concentration of the receptor compound in one or more layers containing the sensitizer compound and the receptor compound.

[0433] In some embodiments, the S1 energy of the first host is greater than the S1 energy of the acceptor compound. In some embodiments, the T1 energy of the first host is greater than the T1 energy of the sensitizer compound. In some embodiments, the HOMO energy of the sensitizer compound is greater than the HOMO energy of the acceptor compound. In some embodiments, the HOMO energy level of the second host is shallower than the HOMO energy level of the acceptor compound. In some embodiments, the HOMO energy level of the acceptor compound is deeper than at least one selected from the sensitizer compound and the first host.

[0434] In some embodiments, the first host and / or the second host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, azaborane, oxaborabine, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene). In some embodiments, the first host and the second host are both organic compounds.

[0435] In some embodiments, at least one of the first host and the second host is a metal complex. In some embodiments, each of the first host and / or the second host is independently selected from the group consisting of structures in Host Group 1 below.

[0436]

[0437]

[0438]

[0439]

[0440]

[0441]

[0442] in:

[0443] Each of J1 to J6 is independently C or N;

[0444] L' is a direct bond or an organic linking group;

[0445] Each Y AA , Y BB , Y CC and Y DD independently selected from the group consisting of: absent, one bond, direct bond, O, S, Se, CRR', SiRR', GeRR', NR, BR, BRR';

[0446] R A '、R B '、R C '、R D '、R E '、R F ' and R G Each of ' independently represents a single substitution up to the maximum substitution, or no substitution;

[0447] Each R, R', R A '、R B '、R C '、R D '、R E '、R F ' and R G ' is independently hydrogen or a substituent selected from the group consisting of general substituents defined herein; any two substituents may be joined or fused to form a ring;

[0448] Also, where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

[0449] In some embodiments, at least one of J1 to J3 is N; in some embodiments, at least two of J1 to J3 are N; in some embodiments, all three of J1 to J3 are N. In some embodiments, each Y CC and Y DD O, S and SiRR' are preferred, and O or S is more preferred. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced by N to form a nitrogen heterocycle.

[0450] In order to reduce the amount of Dexter energy transfer between the sensitizer compound and the acceptor compound, a larger distance is preferred between the mass center of the sensitizer compound and the mass center of the closest acceptor compound in the emission region. Thus, in some embodiments, the distance between the mass center of the acceptor compound and the mass center of the sensitizer compound is at least 2, 1.5, 1.0, or 0.75 nm.

[0451] Preferred acceptor / sensitizer VDR combinations (A): In some embodiments, it is preferred that the VDR of the acceptor is less than 0.33 compared to the isotropic emitter in order to reduce the coupling of the transition dipole moment of the emitting acceptor to the plasma mode in order to achieve higher outcoupling efficiency. In some cases, when the VDR of the acceptor is less than 0.33, it is preferred that the VDR of the sensitizer is less than 0.33 in order to improve the coupling of the transition dipole moments of the sensitizer and the acceptor, thereby optimizing the Forster energy transfer rate. Thus, in some embodiments of the present OLED, the acceptor compound in the present OLED exhibits a VDR value equal to or less than 0.33, 0.30, 0.25, 0.2, 0.15, 0.10, 0.08, or 0.05 when the VDR is measured using an emitting film test sample having the acceptor compound as the sole emitter; and the sensitizer compound in the present OLED exhibits a VDR value equal to or less than 0.33, 0.30, 0.25, 0.2, 0.15, 0.10, 0.08, or 0.05 when the VDR is measured using an emitting film test sample having the sensitizer compound as the sole emitter.

[0452] Preferred Acceptor / Sensitizer VDR Combinations (B): In some embodiments, it is preferred that the VDR of the acceptor is less than 0.33 compared to the isotropic emitter in order to reduce the coupling of the transition dipole moment of the emitting acceptor to the plasma mode, thereby achieving higher outcoupling efficiency. In some cases, when the VDR of the acceptor is less than 0.33, it is preferred to minimize the intermolecular interactions between the sensitizer and the acceptor to reduce the degree of Dexter quenching. By changing the molecular geometry of the sensitizer to reduce the intermolecular interactions, it may be preferred that the sensitizer has a VDR greater than 0.33. Thus, in some embodiments of the present OLED, the acceptor compound in the present OLED exhibits a VDR value equal to or less than 0.33, 0.30, 0.25, 0.2, 0.15, 0.10, 0.08, or 0.05 when the VDR is measured using an emitting thin film test sample having the acceptor compound as the sole emitter; and the sensitizer compound in the present OLED exhibits a VDR value greater than 0.33, 0.4, 0.5, 0.6, or 0.7 when the VDR is measured using an emitting thin film test sample having the sensitizer compound as the sole emitter.

[0453] Preferred Acceptor / Sensitizer VDR Combinations (C): In some embodiments, it is preferred that the VDR of the acceptor is greater than 0.33 compared to an isotropic emitter in order to increase the coupling of the transition dipole moment of the acceptor to the plasma mode, thereby reducing the transient lifetime of the excited state in the emissive layer. In some cases, increased coupling to the plasma mode can be combined with an enhancement layer in a plasma OLED device to increase efficiency and extend operating lifetime. In some cases, when the VDR of the acceptor is greater than 0.33, it is preferred to minimize the intermolecular interactions between the sensitizer and the acceptor to reduce the extent of Dexter quenching. By changing the molecular geometry of the sensitizer to reduce intermolecular interactions, it can be preferred that the sensitizer has a VDR less than 0.33. Thus, in some embodiments of the present OLED, the acceptor compound in the present OLED exhibits a VDR value greater than 0.33, 0.4, 0.5, 0.6, or 0.7 when the VDR is measured using an emitting film test sample having the acceptor compound as the sole emitter; and the sensitizer compound in the present OLED exhibits a VDR value equal to or less than 0.33, 0.30, 0.25, 0.2, 0.15, 0.10, 0.08, or 0.05 when the VDR is measured using an emitting film test sample having the sensitizer compound as the sole emitter.

[0454] Preferred acceptor / sensitizer VDR combinations (D): In some embodiments, it is preferred that the VDR of the acceptor is greater than 0.33 compared to an isotropic emitter in order to increase the coupling of the transition dipole moment of the acceptor to the plasma mode, thereby reducing the transient lifetime of the excited state in the emissive layer. In some cases, increased coupling to the plasma mode can be combined with an enhancement layer in a plasma OLED device to increase efficiency and extend operating lifetime. In some cases, when the VDR of the acceptor is less than 0.33, it is preferred that the VDR of the sensitizer is greater than 0.33 in order to improve the coupling of the transition dipole moments of the sensitizer and the acceptor, thereby optimizing the Forster energy transfer rate. Thus, in some embodiments of the present OLED, the acceptor compound in the present OLED exhibits a VDR value greater than 0.33, 0.4, 0.5, 0.6, or 0.7 when the VDR is measured using an emitting film test sample having the acceptor compound as the sole emitter; and the sensitizer compound in the present OLED exhibits a VDR value greater than 0.33, 0.4, 0.5, 0.6, or 0.7 when the VDR is measured using an emitting film test sample having the sensitizer compound as the sole emitter.

[0455] VDR is the overall average fraction of vertically oriented molecular dipoles of the luminescent compound in the thin film sample of the emissive layer, where the "vertical" orientation is relative to the surface plane of the substrate on which the thin film sample is formed (i.e., perpendicular to the substrate surface plane). A similar concept is the horizontal dipole ratio (HDR), which is the overall average fraction of horizontally oriented molecular dipoles of the luminescent compound in the thin film sample of the emissive layer, where the "horizontal" orientation is relative to the surface plane of the substrate on which the thin film sample is formed (i.e., parallel to the substrate surface plane). By definition, VDR+HDR=1. VDR can be measured by angle-dependent, polarization-dependent photoluminescence measurements. The VDR of the emissive layer of the thin film test sample can be determined by comparing the measured emission pattern of the light-excited thin film test sample as a function of polarization with the computer-modeled pattern. For example, Figure 3 Modeled data for p-polarized emission are shown in Figure 1. Modeled p-polarized angular photoluminescence (PL) for emitters with different VDRs are plotted. Modeled PL peaks are observed in p-polarized PL around an angle of 45 degrees, where the peak PL is larger when the VDR of the emitter is higher.

[0456] To measure the VDR value of a thin film test sample, the thin film test sample can be formed using the acceptor compound or the sensitizer compound (depending on whether the VDR of the acceptor compound or the sensitizer compound is measured) as the only emitter in the thin film and using the reference host compound A as the host. Preferably, the reference host compound A is The thin film test sample is formed by thermally evaporating the emitter compound and the host compound on the substrate. For example, the emitter compound and the host compound can be co-evaporated. In some embodiments, the doping level of the emitter compound in the host can be 0.1 wt.% to 50 wt.%. In some embodiments, for a blue emitter, the doping level of the emitter compound in the host can be 3 wt.% to 20 wt.%. In some embodiments, for red and green emitters, the doping level of the emitter compound in the host can be 1 wt.% to 15 wt.%. The thermally evaporated thin film test sample can have a thickness of 50 to 100 wt.%. Thickness.

[0457] In some embodiments, the OLED of the present disclosure may include a sensitizer, an acceptor, and one or more hosts in the emission region, and the preferred acceptor / sensitizer VDR combinations (A)-(D) mentioned above are still applicable. In these embodiments, the VDR value of the acceptor compound can be measured with a thin film test sample formed by one or more hosts and acceptors, wherein the acceptor is the only emitter in the thin film test sample. Similarly, the VDR value of the sensitizer compound can be measured with a thin film test sample formed by one or more hosts and sensitizers, wherein the sensitizer is the only emitter in the thin film test sample.

[0458] In use to produce Figure 3 In the example of , a 30 nm thick film of material has a refractive index of 1.75 and the emission is monitored in a semi-infinite medium with a refractive index of 1.75. Each curve is normalized to the photoluminescence intensity of 1 (at an angle of zero degrees perpendicular to the film surface). As the VDR of the emitter changes, the peak around 45 degrees increases substantially. When the software is used to fit the VDR of experimental data, the modeled VDR will change until the difference between the modeled and experimental data is minimized.

[0459] Since VDR represents the average dipole orientation of the luminescent compound in the film sample, even if there are other compounds with emission capability in the emission layer, if they do not contribute to light emission, the VDR measurement does not reflect their VDR. In addition, by including a host material that interacts with the luminescent compound, the VDR of the luminescent compound can be adjusted. Therefore, the luminescent compound in the film sample with host material A will show a VDR measurement value, and the same luminescent compound in the film sample with host material B will show different VDR measurements. In addition, in some embodiments, an excimer or quasi-molecule in an emission state is required to be formed between two adjacent molecules. The VDR of these emission states may be different from when the only component in the excimer or quasi-molecule emits or is present in the sample.

[0460] In some embodiments, the OLED is a plasmonic OLED. In some embodiments, the OLED is a waveguide OLED.

[0461] In some embodiments, the emission region may further include a second host. In some embodiments, the second host includes a moiety selected from the group consisting of: bicarbazole, indolecarbazole, triazine, pyrimidine, pyridine, and borane. In some embodiments, the HOMO energy level of the second host is shallower than the HOMO energy level of the acceptor compound.

[0462] In some embodiments, the OLED emits white light at room temperature when a voltage is applied across the device.

[0463] In some embodiments, the OLED emits luminescent radiation at room temperature when a voltage is applied across the device; wherein the first radiative luminescent component is composed of a light emitting component λ max1 The first radiation component is independently contributed by an acceptor compound selected from the group consisting of: greater than 340 nm to equal to or less than 500 nm, greater than 500 nm to equal to or less than 600 nm, and greater than 600 nm to equal to or less than 900 nm. In some embodiments, the FWHM of the first radiation component is 50, 40, 35, 30, 25, 20, 15, 10 or 5 nm or less. In some embodiments, the first radiation component has a 10% onset of an emission peak less than 465, 460, 455 or 450 nm.

[0464] In some embodiments, the sensitizer compound is partially or fully deuterated. In some embodiments, the acceptor compound is partially or fully deuterated. In some embodiments, the first body is partially or fully deuterated. In some embodiments, the second body is partially or fully deuterated.

[0465] In some embodiments, the sensitizer compound S1 and / or the receptor each independently comprises at least one substituent having a secondary sphericity greater than or equal to 0.45, 0.55, 0.65, 0.75 or 0.80. Secondary sphericity is a measure of the three dimensions of a bulky group. Secondary sphericity is defined as the ratio between principal moments of inertia (PMI). Specifically, secondary sphericity is the ratio of three times PMI1 to the sum of PMI1, PMI2 and PMI3, wherein PMI1 is the minimum principal moment of inertia, PMI2 is the second minimum principal moment of inertia, and PMI3 is the maximum principal moment of inertia. The secondary sphericity of the lowest energy conformation of the structure can be calculated after optimizing the ground state using density functional theory. More detailed information can be found in paragraphs

[0054] to

[0059] of U.S. Application No. 18 / 062,110 (filed on December 6, 2022), the contents of which are incorporated herein by reference. In some embodiments, the sensitizer compound S1 and / or the receptor each independently comprises a van der Waals volume greater than 153, 206, 259, 290, or In some embodiments, the sensitizer compound S1 and / or the receptor each independently comprises at least one substituent having a molecular weight greater than 167, 187, 259, 303, or 305 amu.

[0466] In some embodiments, one of the first and second hosts is a hole transport host and the other of the first and second hosts is an electron transport host. In some embodiments, the first host is a hole transport host; and wherein the first host comprises at least one chemical group selected from the group consisting of: amino, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, and 5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole. In some embodiments, the first host is an electron transport host; and wherein the first host comprises at least one chemical group selected from the group consisting of pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, aza-triphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, 5,9-dioxa-13b-borazinnaphtho[3,2,1-de]anthracene, borane, nitrile, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene). In some embodiments, one of the first and second hosts is a bipolar host comprising a hole transport moiety and an electron transport moiety.

[0467] In some embodiments, the OLED further comprises a color changing layer or a color filter.

[0468] In some embodiments, the formulation may comprise at least two different compounds of the following: a sensitizer compound, a receptor compound, and a host.

[0469] In some embodiments, the chemical structure is selected from the group consisting of: a monomer, a polymer, a macromolecule, and a supramolecule, wherein the chemical structure comprises at least two of the following components: a sensitizer compound, a receptor compound, and a host.

[0470] In some embodiments, the premixed co-evaporation source is a mixture of a first compound and a second compound; wherein the co-evaporation source is a co-evaporation source for a vacuum deposition process or an OVJP process; wherein the first compound and the second compound are differently selected from the group consisting of: a sensitizer compound, a receptor compound, a first host compound and a second host compound; wherein the first compound has an evaporation temperature T1 of 150 to 350° C.; wherein the second compound has an evaporation temperature T2 of 150 to 350° C.; wherein the absolute value of T1-T2 is less than 20° C.; wherein the first compound has a concentration C1 in the mixture and a concentration C2 in a test film formed by depositing the mixture in a vacuum deposition tool, on a surface positioned at a predefined distance relative to the evaporated mixture, on a 1×10 -6 Torr to 1×10 -9 Torr constant pressure, The mixture further comprises a third compound; wherein the third compound is different from the first and second compounds and is selected from the same group 1; wherein the third compound has an evaporation temperature T3 of 150 to 350°C, and wherein the absolute value of T1-T3 is less than 20°C.

[0471] In some embodiments, the first compound has an evaporation temperature T1 of 200 to 350°C and the second compound has an evaporation temperature T2 of 200 to 350°C. In some embodiments, the absolute value of (C1-C2) / C1 is less than 3%. In some embodiments, the vapor pressure P1 of the first compound at T1 is 1atm, and the vapor pressure P2 of the second compound at T2 is 1atm; and wherein the ratio of P1 / P2 is in the range of 0.90:1 to 1.10:1. In some embodiments, the first compound has a first mass loss rate and the second compound has a second mass loss rate, wherein the ratio between the first mass loss rate and the second mass loss rate is in the range of 0.90:1 to 1.10:1, 0.95:1 to 1.05:1, or 0.97:1 to 1.03:1. In some embodiments, the first compound and the second compound each have a purity of more than 99% as determined by high pressure liquid chromatography. In some embodiments, the composition is in liquid form at a temperature less than the lower of T1 and T2.

[0472] In some embodiments, a method of manufacturing an organic light-emitting device may include: providing a substrate having a first electrode disposed thereon; depositing a first organic layer on the first electrode by evaporating a premixed co-evaporation source in a high vacuum deposition tool, wherein the premixed co-evaporation source is a mixture of the first compound and the second compound described above, wherein the high vacuum deposition tool has a 1×10 -6 Torr to 1×10 -9and depositing a second electrode on the first organic layer.

[0473] It should be understood that all compound and device embodiments described herein are interchangeable if those embodiments are also applicable in different aspects of the overall disclosure.

[0474] In some embodiments, each of the sensitizer compound S1, the receptor, and the host compound described herein may be at least 10% deuterated, at least 20% deuterated, at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, the percentage of deuteration has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., positions of hydrogen or deuterium) replaced by deuterium atoms.

[0475] C. Other Aspects of the Disclosed OLEDs

[0476] In some embodiments, the OLED may further comprise another host, wherein the another host comprises a benzo-fused thiophene or benzo-fused furan containing triphenylene, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: C n H 2n+1 , OC n H 2n+1 、OAr1、N(C n H 2n+1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar1、Ar1-Ar2、C n H 2n -Ar1 or unsubstituted, wherein n is an integer from 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole and heteroaromatic analogs thereof.

[0477] In some embodiments, the additional host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolecarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ 2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-borazinonaphtho[3,2,1-de]anthracene, azaborane, oxaborabine, dihydroacridine, xanthene, dihydrobenzazasilane, dibenzooxasilane, phenoxazine, phenoxathiol, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrol, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, borane, silane, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ 2 -benzo[d]benzo[4,5]imidazo[3,2-a]imidazole and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

[0478] In some embodiments, the another subject may be selected from the group consisting of:

[0479]

[0480]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487] Aza-substituted variants thereof, fully or partially deuterated variants thereof, and combinations thereof.

[0488] In some embodiments, the other host comprises a metal complex.

[0489] In some embodiments, the additional host is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 of formula EGa-MGb-EGc, or when MGb is absent, EG1-EG1 to EG53-EG53 of formula EGa-EGc, wherein a is an integer from 1 to 53, b is an integer from 1 to 27, and c is an integer from 1 to 53. The structures of EG1 to EG53 are shown below:

[0490]

[0491]

[0492] The structures of MG1 to MG27 are as follows:

[0493] In the MGb structures shown above, the two bonding positions in the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.

[0494] In some embodiments, the host can be any of its aza-substituted variants, fully or partially deuterated variants, and combinations thereof. In some embodiments, the host has the formula EGa-MGb-Egc and is selected from the group consisting of h1 to h112 as defined in the following List of Host Group 2, wherein each of MGb, EGa, and EGc is defined as follows:

[0495]

[0496]

[0497] In the above table, EGa and EGc structures bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24 and MG25 are annotated with a numerical prefix indicating their bonding position in the MGb structure.

[0498] In yet another aspect, an OLED of the present disclosure may further comprise an emissive region containing a formulation as disclosed in the above compounds section of the present disclosure.

[0499] In some embodiments, the emissive region is comprised of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of: 350, 400, 450, 500, 550, 600, 650, and In some embodiments, at least one of the one or more organic layers is formed of an emissive system having a figure of merit (FOM) equal to or greater than a value selected from the group consisting of: 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM can be found in U.S. Patent Application Publication No. 2023 / 0292605, and the entire contents are incorporated herein by reference. In some embodiments, at least one of the one or more organic layers comprises a compound or formulation of a compound disclosed in Sections A and D of the present disclosure.

[0500] In some embodiments, the OLED or emission region disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such a device includes at least one pixel, wherein the at least one pixel includes a first sub-pixel and a second sub-pixel. The first sub-pixel includes a first OLED including a first emission region. The second sub-pixel includes a second OLED including a second emission region. In some embodiments, the first OLED and / or the second OLED, the first emission region and / or the second emission region may be the same or different and each may independently have various device features and various embodiments of the compounds of the present invention included therein, as well as various combinations and sub-combinations of various device features and various embodiments of the compounds of the present invention included therein, as disclosed herein.

[0501] In some embodiments, the first emission region is configured to emit a wavelength having a peak wavelength λ max1 The second emission region is configured to emit light having a peak wavelength λ max2 In some embodiments, the peak wavelength λ max1 With λ max2 The difference between the two is at least 4 nm, but within the same color. For example, light blue and dark blue light are as described above. In some embodiments, the first emission region is configured to emit a peak wavelength λ max1 Light in one region of the visible spectrum of 400-500nm, 500-600nm, 600-700nm; and the second emission region is configured to emit a peak wavelength λ max2 Light in one of the remaining regions of the visible spectrum of 400-500nm, 500-600nm, 600-700nm. In some embodiments, the first emission region comprises a first number of emission layers, and if there are more than one emission layer, one layer is deposited above another layer; and the second emission region comprises a second number of emission layers, and if there are more than one emission layer, one layer is deposited above another layer; and the first number is different from the second number. In some embodiments, both the first emission region and the second emission region comprise phosphorescent materials, which may be the same or different. In some embodiments, the first emission region comprises a phosphorescent material, and the second emission region comprises a fluorescent material. In some embodiments, both the first emission region and the second emission region comprise fluorescent materials, which may be the same or different.

[0502] In some embodiments, at least one pixel in an OLED or an emission region includes a total of N subpixels; wherein the N subpixels include a first subpixel and a second subpixel; wherein each of the N subpixels includes an emission region; wherein the total number of emission regions within at least one pixel is equal to or less than N-1. In some embodiments, the second emission region is exactly the same as the first emission region; and each subpixel of at least one pixel includes an emission region that is the same as the first emission region. In some embodiments, a full-color pixel arrangement may have a plurality of pixels including a first pixel region and a second pixel region; wherein at least one display feature in the first pixel region is different from a corresponding display feature in the second pixel region, and wherein at least one display feature is selected from the group consisting of: resolution, cavity mode, color, outcoupling, and color filter.

[0503] In some embodiments, the OLED is a stacked OLED comprising one or more charge generation layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emission region disposed above the first electrode, a first CGL disposed above the first emission region, a second emission region disposed above the first CGL, and a second electrode disposed above the second emission region. In some embodiments, the first emission region and / or the second emission region may have the various device features described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white. In some embodiments, one or more emission regions in the pixelated OLED or stacked OLED include a sensitizer and an acceptor, which have various sensitizing device features and various embodiments of the compounds of the present invention disclosed herein. For example, the first emission region is included in the sensitizing device, while the second emission region is not included in the sensitizing device; in some cases, both the first emission region and the second emission region are included in the sensitizing device.

[0504] In some embodiments, the OLED may emit at least 1%, 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% of the light having a plasmon mode. In some embodiments, at least one of the anode, cathode, or a new layer disposed above the organic emission layer is used as an enhancement layer. The enhancement layer comprises a plasmon material exhibiting a surface plasmon resonance, the plasmon material non-radiatively couples with the emitter material, and transfers excited state energy from the emitter material to a non-radiative mode of a surface plasmon polariton. In some embodiments, the enhancement layer is disposed at a distance from the organic emission layer that does not exceed a threshold distance, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. The threshold distance is the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and the total radiative decay rate constant is equal to the photoluminescence yield of the emitting material in the absence of the enhancement layer.

[0505] In some embodiments, at least one of the anode, cathode, or new layer disposed above the organic emission layer is used as an enhancement layer. The enhancement layer includes a plasmon material that exhibits a surface plasmon resonance, the plasmon material non-radiatively couples to the emitter material, and transfers excited state energy from the emitter material to a non-radiative mode of a surface plasmon polariton. The enhancement layer is arranged to be no more than a threshold distance from the organic emission layer, wherein due to the presence of the enhancement layer, the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant, and the threshold distance is the position where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further includes an outcoupling layer. In some embodiments, the outcoupling layer is disposed above the enhancement layer on the opposite side of the organic emission layer. In some embodiments, the outcoupling layer is disposed on the side of the emission layer opposite to the enhancement layer, but can still outcouple energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from the surface plasmon modes of the device into other modes, such as but not limited to organic waveguide modes, substrate modes, or another waveguide mode. If energy is scattered into non-free space modes of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and / or mixtures of these materials.

[0506] The enhancement layer changes the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, changed emission line shape, variation in emission intensity with angle, changed emitter material stability, changed OLED efficiency, and reduced roll-off efficiency of the OLED device. Placing the enhancement layer on the cathode side, the anode side, or both, or using the enhancement layer itself as a CGL, produces an OLED device that utilizes any of the above effects. In addition to the specific functional layers described in the various OLED examples mentioned herein and shown in the figures, the OLED according to the present disclosure may also include any other functional layers commonly found in OLEDs.

[0507] The enhancement layer may comprise a plasmonic material, an optically active metamaterial, or a hyperbolic metamaterial. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may comprise at least one of the following: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials, where the effect of the medium as a whole is different from the sum of its material parts. Specifically, we define an optically active metamaterial as a material that has both negative permittivity and negative permeability. On the other hand, a hyperbolic metamaterial is an anisotropic medium in which the permittivity or permeability has different signs for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures, such as distributed Bragg reflectors (DBRs), because the medium should appear uniform in the propagation direction on the length scale of the light wavelength. Using terminology that can be understood by those skilled in the art: the dielectric constant of the metamaterial in the propagation direction can be described by the effective dielectric approximation. Plasmonic materials and metamaterials provide methods for controlling light propagation, which can enhance OLED performance in many ways.

[0508] In some embodiments, the enhancement layer is arranged as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features arranged periodically, quasi-periodically, or randomly, or has sub-wavelength-sized features arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and sub-wavelength-sized features have sharp edges.

[0509] In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or has sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer can be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed above a material. In these embodiments, the outcoupling can be adjusted by at least one of: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the enhancement layer, and / or changing the material of the enhancement layer. The plurality of nanoparticles of the device can be formed of at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials, and / or a core of one type of material and coated with a shell of another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. Multiple nanoparticles can have additional layers disposed above them. In some embodiments, the outcoupling layer can be used to adjust the polarization of the emission. Changing the size and periodicity of the outcoupling layer can select the polarization type that is preferentially outcoupled to air. In some embodiments, the outcoupling layer also acts as an electrode of the device.

[0510] In some embodiments of plasmonic devices, the emitter and / or host compound used in the emissive layer has a vertical dipole ratio (VDR) of 0.33 or greater. In some such embodiments, the emitter and / or host compound has a VDR of 0.40, 0.50, 0.60, 0.70, or greater.

[0511] In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED), the organic light-emitting device having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the present disclosure.

[0512] In some embodiments, a consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a formulation as described herein.

[0513] In some embodiments, the consumer product can be one of the following: a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior lighting and / or signaling, a head-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cellular telephone, a tablet computer, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay having a diagonal of less than 2 inches, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

[0514] In general, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an electric current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When electrons and holes are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair with an excited energy state. When the exciton relaxes through a light emission mechanism, light is emitted. In some cases, the exciton can be localized on an excimer or an excited complex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

[0515] Several OLED materials and configurations are described in US Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

[0516] The first OLEDs used emissive molecules that emitted light from a singlet state ("fluorescence"), as disclosed, for example, in US Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in a time frame of less than 10 nanoseconds.

[0517] Recently, OLEDs with emissive materials that emit light from triplet states ("phosphorescence") have been demonstrated. Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices", Nature, Vol. 395, 151-154, 1998 ("Baldo-I"); and Baldo et al., "Very high-efficiency green organic light-emitting devices based on electrophosphorescence", Appl. Phys. Lett., Vol. 75, Nos. 3, 4-6 (1999) ("Baldo-II"), which are incorporated by reference in their entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, Columns 5-6, which is incorporated by reference.

[0518] Figure 1 An organic light-emitting device 100 is shown. The figure is not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emission layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. The cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 can be manufactured by depositing the layers in sequence. The properties and functions of these various layers and example materials are described in more detail in US 7,279,704, columns 6-10, which are incorporated by reference.

[0519] More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated by reference in its entirety. U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes comprising a composite cathode having a thin layer of a metal (e.g., Mg:Ag) with an overlying transparent, conductive, sputter-deposited ITO layer. The theory and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174116, which is incorporated by reference in its entirety.

[0520] Figure 2 An inverted OLED 200 is shown. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 can be manufactured by depositing the layers in order. Because the most common OLED configuration has a cathode disposed above the anode, and device 200 has cathode 215 disposed below anode 230, device 200 can be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 An example is provided of how some layers may be omitted from the structure of device 100 .

[0521] Figure 1 and 2The simple layered structures described in are provided by way of non-limiting examples, and it should be understood that embodiments of the present disclosure may be used in conjunction with various other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than the specifically described materials may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that a combination of materials may be used, such as a mixture of a host and a dopant, or more generally, a mixture. In addition, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, the OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise, for example, Figure 1 and 2 Multiple layers of said different organic materials.

[0522] Structures and materials not specifically described may also be used, such as OLEDs containing polymeric materials (PLEDs), such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of another example, an OLED having a single organic layer may be used. OLEDs may be stacked, such as described in U.S. Pat. No. 5,707,745 to Forrest et al., which is incorporated by reference in its entirety. OLED structures may deviate from Figure 1 and 2 For example, the substrate may include angled reflective surfaces to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and / or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entirety.

[0523] The device manufactured according to the embodiment of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrode and the organic layer from being damaged when exposed to harmful substances in an environment including moisture, steam and / or gas, etc. The barrier layer can be deposited on a substrate, an electrode, under a substrate, an electrode, or beside a substrate, an electrode, or on any other part (including an edge) of the device. The barrier layer may include a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques, and may include a composition having a single phase and a composition having multiple phases. Any suitable material or material combination may be used for the barrier layer. The barrier layer may be incorporated into an inorganic compound or an organic compound or both. A preferred barrier layer comprises a mixture of a polymer material and a non-polymer material, as described in U.S. Patent No. 7,968,146, PCT Patent Application No. PCT / US2007 / 023098 and No. PCT / US2009 / 042829, which are incorporated herein by reference in their entirety. In order to be considered a "mixture", the aforementioned polymer and non-polymer materials constituting the barrier layer should be deposited under the same reaction conditions and / or deposited simultaneously. The weight ratio of the polymer material relative to the non-polymer material can be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material can be produced from the same precursor material. In one example, the mixture of the polymeric material and the non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

[0524] The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of electronic component modules (or units), which can be incorporated into a variety of electronic products or intermediate components. Examples of the electronic products or intermediate components include display screens, lighting devices (such as discrete light source devices or lighting panels), etc. that can be utilized by end-user product manufacturers. The electronic component module may optionally include driving electronic devices and / or power supplies. The device manufactured according to the embodiments of the present disclosure can be incorporated into a variety of consumer products, and the consumer products have one or more electronic component modules (or units) incorporated therein. A consumer product comprising an OLED is disclosed, and the OLED includes a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product containing one or more of one or more light sources and / or a certain type of visual display. Some examples of consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior lighting and / or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, phones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays (displays with a diagonal of less than 2 inches), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, light therapy devices, and signage. Various control mechanisms can be used to control devices manufactured according to the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18°C ​​to 30°C, and more preferably at room temperature (20-25°C), but can be used outside this temperature range (e.g., -40°C to +80°C).

[0525] More details regarding OLEDs and the definitions set forth above can be found in U.S. Patent No. 7,279,704, which is incorporated herein by reference in its entirety.

[0526] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can employ the materials and structures. More generally, organic devices such as organic transistors can employ the materials and structures.

[0527] In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, rollable, foldable, stretchable, and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.

[0528] In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of ​​less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of ​​at least 50 square inches. In some embodiments, the OLED is a lighting panel.

[0529] According to another aspect, a formulation comprising a compound described herein is also disclosed.

[0530] The OLEDs disclosed herein may be incorporated into one or more of consumer products, electronic component modules, and lighting panels.The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, while the compound may be a non-emissive dopant in other embodiments.

[0531] In another aspect of the present invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may include one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

[0532] The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or their monovalent or multivalent variants. In other words, the compounds of the present invention or their monovalent or multivalent variants can be part of a larger chemical structure. Such chemical structures can be selected from the group consisting of: monomers, polymers, macromolecules, and supramolecules (also referred to as supramolecules). As used herein, a "monovalent variant of a compound" refers to a portion that is identical to the compound but one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a "multivalent variant of a compound" refers to a portion that is identical to the compound but more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of a supramolecule, the compounds of the present invention can also be incorporated into a supramolecular complex without covalent bonds.

[0533] F. Combinations of Compounds of the Disclosure with Other Materials

[0534] The materials described herein as being suitable for use in a particular layer in an organic light-emitting device can be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0535] a) Conductive dopants:

[0536] The charge transport layer can be doped with a conductivity dopant to substantially change its charge carrier density, which in turn will change its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor can also be achieved. The hole transport layer can be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

[0537] Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.

[0538]

[0539]

[0540] b)HIL / HTL:

[0541] The hole injection / transport material used in the present disclosure is not particularly limited, and any compound can be used as long as the compound is generally used as a hole injection / transport material. Examples of the material include (but are not limited to): phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolecarbazole derivatives; polymers containing fluorocarbons; polymers having a conductive dopant; conductive polymers such as PEDOT / PSS; self-assembling monomers derived from compounds such as phosphonic acid and silane derivatives; metal oxide derivatives such as MoOx ; p-type semiconductive organic compounds, such as 1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile; metal complexes; and crosslinkable compounds.

[0542] Examples of aromatic amine derivatives for use in HIL or HTL include, but are not limited to, the following general structure:

[0543]

[0544] Ar 1 To Ar 9 Each of the following is selected from the group consisting of aromatic hydrocarbon cyclic compounds: benzene, biphenyl, terphenyl, triphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each Ar may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0545] In one aspect, Ar 1 To Ar 9 Independently selected from the group consisting of:

[0546]

[0547] Where k is an integer from 1 to 20; X 101 To X 108 is C (including CH) or N; Z 101 It is NAr1 , O or S; Ar 1 Having the same groups as defined above.

[0548] Examples of metal complexes used in HIL or HTL include, but are not limited to, the following general formula:

[0549]

[0550] Where Met is a metal with an atomic weight greater than 40; (Y 101 -Y 102 ) is a bidentate ligand, Y 101 and Y 102 is independently selected from C, N, O, P and S; L 101 is an auxiliary ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0551] In one aspect, (Y 101 -Y 102 ) is a 2-phenylpyridine derivative. In another aspect, (Y 101 -Y 102 ) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os and Zn. In another aspect, the metal complex has a relative + / Fc coupling has a minimum oxidation potential in solution of less than about 0.6 V.

[0552] Non-limiting examples of HIL and HTL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, J P2007091719, JP2008021687, JP2014-009196, KR20110088898, KR2013007 7473, TW201139402, US06517957, US20020158242, US20030162053, US2005 0123751, US20060182993, US20060240279, US20070145888, US2007018187 4. US20070278938, US20080014464, US20080091025, US20080106190, US200 80124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US201 1007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, US5061569, US5639914, WO0 5075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO201 3087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO 2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921,WO2014034791, WO2014104514, WO2014157018. ,

[0553]

[0554]

[0555]

[0556]

[0557]

[0558] c) EBL:

[0559] An electron blocking layer (EBL) can be used to reduce the number of electrons and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can produce substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to desired areas of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

[0560] d) Subject:

[0561] The light-emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of host materials are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than the triplet energy of the dopant. Any host material may be used with any dopant as long as the triplet criterion is satisfied.

[0562] Examples of metal complexes used as hosts preferably have the following general formula:

[0563]

[0564] Where Met is a metal; (Y 103 -Y 104 ) is a bidentate ligand, Y 103 and Y 104 is independently selected from C, N, O, P and S; L 101is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal; and k'+k" is the maximum number of ligands that can be attached to the metal.

[0565] In one aspect, the metal complex is:

[0566]

[0567] where (ON) is a bidentate ligand with a metal coordinated to O and N atoms.

[0568] In another aspect, Met is selected from Ir and Pt. In another aspect, (Y 103 -Y 104 ) is a carbene ligand.

[0569] In one aspect, the host compound contains at least one selected from the following group: a group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furanodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units, which are groups of the same type or different types selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are directly or via at least one of oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units and aliphatic ring groups. Each option in each group may be unsubstituted or substituted with a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

[0570] In one aspect, the subject compound contains at least one of the following groups in the molecule:

[0571]

[0572]

[0573] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition to Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X 101 To X 108 Z is independently selected from C (including CH) or N. 101 and Z 102 Independently selected from NR 101 , O or S.

[0574] Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US2009 0017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, U S20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO200 6114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO20090 86028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133 649. WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, US9466803,

[0575]

[0576]

[0577]

[0578]

[0579]

[0580] e) Other emitters:

[0581] One or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is commonly used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emission via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-type delayed fluorescence), triplet-triplet annihilation, or a combination of these processes.

[0582] Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP201310263, JP4478555, KR1020090133652, KR20120090133653. 32054, KR20130043460, TW201332980, US06699599, US06916554, US200100 19782, US20020034656, US20030068526, US20030072964, US20030138657, U U.S. 20060202194, US20060251923, US20070034863, US20070087321, US200701 03060, US20070111026, US20070190359, US20070231600, US2007034863, US 2007104979, US2007104980, US2007138437, US2007224450, US2007278936 , US20080020237, US20080233410, US20080261076, US20080297033, US2008 05851, US2008161567, US2008210930, US20090039776, US20090108737, US 20090115322, US20090179555, US2009085476, US2009104472, US201000905 91. US20100148663, US20100244004, US20100295032, US2010102716, US20 10105902, US2010244004, US2010270916, US20110057559, US20110108822,US20110204333、US2011215710、US2011227049、US2011285275、US2012292601、US20130146848、US2013033172、US2013165653、US2013181190、US2013334521、US20140246656、US2014103305、US6303238、US6413656、US6653654、US6670645、US6687266、US6835469、US6921915、US7279704、US7332232、US7378162、US7534505、US7675228、US7728137、US7740957、US7759489、US7951947、US8067099、US8592586、US8871361、WO06081973、WO06121811、WO07018067、WO07108362、WO07115970、WO07115981、WO08035571、WO2002015645、WO2003040257、WO2005019373、WO2006056418、WO2008054584、WO2008078800、WO2008096609、WO2008101842、WO2009000673、WO2009050281、WO2009100991、WO2010028151、WO2010054731、WO2010086089、WO2010118029、WO2011044988、WO2011051404、WO2011107491、WO2012020327、WO2012163471、WO2013094620、WO2013107487、WO2013174471、WO2014007565、WO2014008982、WO2014023377、WO2014024131、WO2014031977、WO2014038456、WO2014112450。、

[0583]

[0584]

[0585]

[0586]

[0587]

[0588] f)HBL:

[0589] A hole blocking layer (HBL) can be used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can result in substantially higher efficiency and / or longer lifetime than a similar device lacking a blocking layer. In addition, a blocking layer can be used to confine emission to a desired area of ​​the OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and / or a higher triplet energy than one or more of the hosts closest to the HBL interface.

[0590] In one aspect, the compounds used in HBL contain the same molecules or the same functional groups as used in the subjects described above.

[0591] In another aspect, the compound used in HBL contains at least one of the following groups in the molecule:

[0592]

[0593] Where k is an integer from 1 to 20; L 101 is another ligand, and k' is an integer from 1 to 3.

[0594] g)ETL:

[0595] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of ETL materials are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.

[0596] In one aspect, the compound used in the ETL contains at least one of the following groups in the molecule:

[0597]

[0598] Where R 101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition to Ar above. Ar 1 To Ar3 has a similar definition to Ar mentioned above. k is an integer from 1 to 20. 101 To X 108 is selected from C (including CH) or N.

[0599] In another aspect, the metal complex used in the ETL contains (but is not limited to) the following general formula:

[0600]

[0601] wherein (ON) or (NN) is a bidentate ligand having a metal coordinated to atoms O, N or N, N; L 101 is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

[0602] Non-limiting examples of ETL materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below, along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, and US2009018957. 10108990, US2011156017, US2011210320, US2012193612, US2012214993, US201401 4925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO20 07111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO201110 5373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

[0603]

[0604]

[0605]

[0606] h) Charge Generation Layer (CGL)

[0607] In a tandem or stacked OLED, the CGL plays a fundamental role in the performance and consists of an n-doped layer and a p-doped layer for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and electrodes. The electrons and holes consumed in the CGL are refilled by electrons and holes injected from the cathode and anode, respectively; then, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer. In some embodiments, at least one emission region in a tandem or stacked OLED comprises a sensitizing device as described herein.

[0608] In any compound disclosed herein, hydrogen atoms may be partially or fully deuterated. The minimum amount of deuterated hydrogen in a compound is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any specific substituent listed, such as, but not limited to, methyl, phenyl, pyridyl, etc., may be in its non-deuterated, partially deuterated, and fully deuterated form. Similarly, substituent classes (such as, but not limited to, alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in its non-deuterated, partially deuterated, and fully deuterated forms.

[0609] It should be understood that the various embodiments described herein are only for example, and do not wish to limit the scope of the present invention. For example, other materials and structures can be used to replace many materials and structures described herein without departing from the spirit of the present invention. The claimed invention may therefore include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that various theories about why the present invention works do not wish to be restrictive.

[0610] It should also be understood that all compound and device embodiments described herein are interchangeable if those embodiments are also applicable in different aspects of the overall disclosure.

[0611] E. Experimental Section

[0612] To simulate the optical properties of the structure of the present invention, Fluxim Setfos 4.6 simulation software was used. The following PL spectra of the compounds of the present invention and comparative compounds were input into an optical stack comprising: 70 μm glass, followed by 200 nm silver (optical parameters from Setfos software), followed by 10 nm IZO, followed by a variable thickness HTL with a refractive index of 1.78 (see Table 1), followed by a 40 nm EML with a refractive index of 1.78, followed by a 37 nm ETL with a refractive index of 1.7, followed by 18 nm silver, followed by a 65 nm CPL with a refractive index of 1.82, followed by air.

[0613] From a 5% emitter The input PL spectra of the emitters were obtained from vacuum thermal evaporation (VTE) films of H1. The structures of these materials are:

[0614]

[0615] The emission spectra of these emitters have the same peak wavelength (521 nm), but have significantly different emission line shapes with different M / T ratios (see Table 1):

[0616] The results of the top emission simulations are summarized in Table 1 below:

[0617] Emitter PL M / T Ratio Simulated HTL thickness (nm) Simulation 1931CIEx <![CDATA[Simulated l 60 / l0]]> Comparison A 0.37 162 0.21 13％ The present invention A 0.43 165 0.21 18％

[0618] As demonstrated by the results in Table 1, for a given 1931CIEx of 0.21, the combination of the higher M / T ratio of the emitter of the present invention and the device structure of the present invention enables better angular dependence (l 60 / l0). This allows for improved color saturation (1931CIEx) and angle dependence (l 60 / l0) without unnecessary blue-shifting of the emitter, which could compromise device efficiency and lifetime.

Claims

1. An organic electroluminescent device OLED, comprising: anode; cathode; and an emitting region comprising a first emitting layer disposed between the anode and the cathode; wherein the OLED further comprises a microcavity structure; wherein the first emitting layer comprises a first emitter selected from the group consisting of: a phosphorescent emitter and a fluorescent emitter; wherein when a voltage is applied to the OLED, the first emitting layer emits a first luminescent radiation at room temperature; The first emission layer has a photoluminescence spectrum with a peak emission wavelength λ max , a first area T and a second area M; where T is the total integrated area of ​​the photoluminescence spectrum, and M is in λ max -15nm and λ max The integrated area of ​​the photoluminescence spectrum between +15 nm; The OLED has a brightness of 10 at normal incidence and a brightness of 1 at 60 degrees from normal incidence. 60 ;and One of the following conditions is true: (1) The first emitter is a phosphorescent emitter, wherein the M / T ratio is ≥ 0.38 and l 60 / l0≥15%; and (2) The first emitter is a fluorescent emitter, wherein the M / T ratio is ≥ 0.42 and l 60 / l0≥25%.

2. The OLED of claim 1, wherein the first emitter is a phosphorescent emitter and the M / T ratio is greater than 0.44; and / or wherein the first emitter is a fluorescent emitter and the M / T ratio is greater than 0.48; and / or The OLED further comprises a hole transport layer HTL, wherein the HTL has a peak emission wavelength λ max The refractive index is 1.7 to 1.

9.

3. The OLED of claim 1 , wherein each layer between the first emitting layer and the most reflective electrode has a wavelength λ of the peak emission of the first emitter. max having a refractive index of less than 2.0; and / or wherein the average reflectivity of all layers between the first emitting layer and the most reflective electrode is at the peak emission wavelength λ of the first emitter max Less than 2.

0.

4. The OLED according to claim 1, further comprising a hole transport layer HTL, wherein the HTL has a peak emission wavelength λ of the first emitter. max having a refractive index of at least 2.0 at a temperature of 100°C; and / or wherein the average reflectivity of all layers between the anode and the cathode is at the peak emission wavelength λ of the first emitter max The minimum score is 2.

0.

5. The OLED according to claim 1, further comprising a capping layer disposed over an upper portion of one of the anode or the cathode; and / or wherein the capping layer has a thickness greater than 50 nm; and / or wherein the capping layer is at the peak emission wavelength λ of the first emitter. max having a refractive index in the range of 1.7 to 1.9; and / or wherein the OLED further comprises an outcoupling structure; and / or in, At normal incidence, the first emitter contributes at least 50% of the total brightness of the first luminescent radiation emitted by the OLED; and / or wherein the first luminescent radiation is green, yellow, blue or red.

6. The OLED of claim 1 , wherein the first emitter is a metal coordination complex having a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond; and / or wherein the metal is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu; and / or wherein the first emitter is a fluorescent emitter or a delayed fluorescent compound that acts as a thermally activated delayed fluorescent TADF emitter in the OLED at room temperature.

7. The OLED of claim 1, wherein the first emitter has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ; Where L 1 , L 2 and L 3 Can be the same or different; where x is 1, 2, or 3; Where y is 0, 1 or 2; where z is 0, 1 or 2; Where x+y+z is the oxidation state of metal M; Where L 1 Selected from the group consisting of structures in the following ligand list: Where L 2 and L 3 Independently choose freedom and a group consisting of structures in the ligand list; in: T is selected from the group consisting of B, Al, Ga and In; K 1 ' is a direct key or selected from NR e , PR e , O, S and Se; Each Y 1 To Y 13 independently selected from the group consisting of carbon and nitrogen; Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ; R e and R f may be fused or joined to form a ring; Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution; each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two adjacent substituents of may be fused or joined to form a ring or to form a multidentate ligand.

8. The OLED of claim 7, wherein the first emitter has a formula selected from the group consisting of: Ir(L 1 )3、Ir(L 1 )(L 2 )2、Ir(L 1 )2(L 2 )、Ir(L 1 )2(L 3 )、Ir(L 1 )(L 2 )(L 3 ) and Pt(L 1 )(L 2 ); Where L 1 , L 2 and L 3 are different from each other in the Ir compounds; Where L 1 and L 2 may be the same or different in the Pt compound; and Where L 1 and L 2 may be linked to form a tetradentate ligand in the Pt compound.

9. The OLED of claim 7, wherein the first emitter is selected from the group consisting of: in X 96 To X 99 Each of is independently C or N; Each Y 100 Independently selected from the group consisting of NR", O, S and Se; L is independently selected from the group consisting of: direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR”, C=CR”R”’, S=O, SO2, CR”, CR”R”’, SiR”R”’, GeR”R”’, Alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; X 100 and X 200 is independently selected at each occurrence from the group consisting of: O, S, Se, NR" and CR"R"'; Each R 10a , R 20a , R 30a , R 40a and R 50a , R A ”、R B ”、R C ”、R D ”、R E ” and R F ” independently means mono-substituted to maximally substituted, or no substitution; R, R', R", R'', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、R F ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " " is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring.

10. The OLED of claim 1, wherein the first emitter is a delayed fluorescent compound that acts as a thermally activated delayed fluorescent TADF emitter in the OLED at room temperature; and / or wherein the TADF emitter comprises at least one chemical moiety selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole and oxadiazole.

11. The OLED according to claim 10, wherein the first emitting layer further comprises a sensitizer (S1), and the first emitter is an acceptor, the acceptor being a fluorescent emitter; and / or wherein the fluorescent emitter comprises at least one chemical moiety selected from the group consisting of: Aza-substituted variants thereof, fully or partially deuterated variants thereof, and combinations thereof; in: Y F , Y G , Y H and Y I Each of which is independently selected from the group consisting of: BR, NR, PR, O, S, Se, C=O, S=O, SO2, BRR', CRR', SiRR' and GeRR'; X F and X G Each independently selected from the group consisting of C and N; Y F1 To Y F4 Each independently selected from O, S and NR F1 ; R F1 and R 1S to R 9S each independently represents monosubstitution to the maximum possible number of substitutions or no substitution; and R, R', R F , R G , R F1 and R 1S to R 9S each independently is hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and / or wherein the sensitizer (S1) is capable of acting as a phosphorescent emitter in an OLED at room temperature; and / or wherein the sensitizer (S1) is a metal coordination complex having at least one of the following: a metal-carbon bond, a metal-nitrogen bond, or a metal-oxygen bond; and / or wherein the metal is selected from the group consisting of: Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu.

12. The OLED according to claim 11, wherein the sensitizer (S1) has the formula M(L 1 ) x (L 2 ) y (L 3 ) z ; Where L 1 , L 2 and L 3 Can be the same or different; where x is 1, 2, or 3; Where y is 0, 1 or 2; where z is 0, 1 or 2; Where x+y+z is the oxidation state of metal M; Where L 1 Selected from the group consisting of structures in the following ligand list: Where L 2 and L 3 Independently choose freedom and a group consisting of structures in the ligand list; wherein: T is selected from the group consisting of B, Al, Ga and In; K 1 ' is a direct key or selected from NR e , PR e , O, S and Se; Each Y 1 To Y 13 independently selected from the group consisting of carbon and nitrogen; Y'Select from the group consisting of: BR e NR e , PR e ,O,S,Se,C=O,S=O,SO2,CR e R f 、SiR e R f and GeR e R f ; R e and R f may be fused or joined to form a ring; Each R a , R b , R c and R d can independently represent a single substitution to the maximum possible number of substitutions, or no substitution; Each R a1 , R b1 , R c1 , R d1 , R a , R b , R c , R d , R e and R f are independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, sulfinyl, sulfonyl, phosphino, selenanyl, and combinations thereof; and Where R a1 , R b1 , R c1 , R d1 , R a , R b , R c and R d Any two of the may be fused or joined to form a ring or to form a multidentate ligand.

13. The OLED according to claim 11, wherein the sensitizer (S1) has a formula selected from the group consisting of: Ir(L A )3、Ir(L A )(L B )2、Ir(L A )2(L B )、Ir(L A )2(L C )、Ir(L A )(L B )(L C ) and Pt(L A )(L B ); Where L A , L B and L C are different from each other in the Ir compounds; Where L A and L B may be the same or different in the Pt compound; and Where L A and L B may be linked to form a tetradentate ligand in the Pt compound.

14. The OLED according to claim 11, wherein the sensitizer (S1) is selected from the group consisting of: in X 96 To X 99 Each of is independently C or N; Each Y 100 Independently selected from the group consisting of NR", O, S and Se; L is independently selected from the group consisting of: direct bond, BR", BR"R"', NR", PR", O, S, Se, C=O, C=S, C=Se, C=NR”, C=CR”R”’, S=O, SO2, CR”, CR”R”’, SiR”R”’, GeR”R”’, Alkyl, cycloalkyl, aryl, heteroaryl and combinations thereof; X 100 and X 200 is independently selected at each occurrence from the group consisting of: O, S, Se, NR" and CR"R"'; Each R 10a , R 20a , R 30a , R 40a and R 50a , R A ”、R B ”、R C ”、R D ”、R E ” and R F ” independently means mono-substituted to maximally substituted, or no substitution; R, R', R", R'', R 10a , R 11a , R 12a , R 13a , R 20a , R 30a , R 40a , R 50a , R 60 , R 70 , R 97 , R 98 , R 99 , R A1 '、R A2 '、R A ”、R B ”、R C ”、R D ”、R E ”、R F ”、R G ”、R H ”、R I ”、R J ”、R K ”、R L ”、R M ” and R N " " is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silanyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thiol, selenanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and Any two substituents may be fused or joined to form a ring. 15 . A consumer product comprising the organic light-emitting device according to claim 1 .

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